Givaja 2012

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Chemical Society Reviews

www.rsc.org/chemsocrev Volume 41 | Number 1 | 7 January 2012 | Pages 1–524
Published on 29 June 2011 on http://pubs.rsc.org | doi:10.1039/C1CS15092H
Downloaded on 03 August 2012
ISSN 0306-0012
CRITICAL REVIEW
Gonzalo Givaja, Pilar Amo-Ochoa, Carlos J. Gómez-García and Félix Zamora
Electrical conductive coordination polymers
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Cite this: Chem. Soc. Rev., 2012, 41, 115–147
www.rsc.org/csr CRITICAL REVIEW

Electrical conductive coordination polymers
Gonzalo Givaja,a Pilar Amo-Ochoa,a Carlos J. Gómez-Garcı́ab and Félix Zamora*a
Received 6th April 2011
DOI: 10.1039/c1cs15092h
Coordination polymers are currently one of the hottest topics in Inorganic and Supramolecular
Chemistry. This critical review summarizes the current state-of-the-art on electrical conductive
coordination polymers (CPs), also named metal–organic frameworks (MOFs). The data were collected
following two sort criteria of the CPs structure: dimensionality and bridging ligands (151 references).
1. Introduction is somehow based on the properties found between both types

of polymers. Albeit, the general physical and chemical properties
Coordination polymers (CPs) are a family of compounds that of CPs essentially depend on many factors besides the nature
can be considered as the natural extension of coordination of the bridging ligand. In this scenario, other supramolecular
compounds towards polymerization. Accordingly, CPs are polymers using metal complexes as building-blocks can be
formed by the assembly of two different building blocks: the found, for instance those connected by H-bonds (H-bonded
metal entities (metal ion or metal complex fragment) and the frameworks). However these are rather different and more
bridging ligands. Their architectures and dimensionalities are difficult to predict and design and will not be considered in the
defined by the coordinative geometry and capabilities of these scope of this review. Along this review we will use the term CP
two building-blocks. The definitions found in the literature for from the broader definition above mentioned.
coordination polymers (CPs) slightly differ. The broader In the last few years, a large amount of work has been carried
definition considers that a CP is formed connecting the metal out in the synthesis and structural characterisation of CPs.
building blocks by either organic or inorganic bridging ligands. Structural investigation under the term of crystal engineering,
However, some authors limit it to metal entities linked just dealing with structure design and control of the architecture, has
by inorganic ligands and consider as organic–inorganic become a hot topic in this field. This structural control has
hybrid material those polymers formed by metals connected produced a considerable improvement of the properties associated
through organic ligands. The justification for this differentiation with these materials. Most of these works have focused on the
study of properties such as catalysis, chirality, luminescence,
a
Departamento de Quı´mica Inorgánica, Universidad Autónoma de magnetism, spin-transition (spin-crossover), non-linear optics
Madrid, 28049 Madrid, Spain. E-mail: felix.zamora@uam.es; (NLO), porosity or zeolitic-like behaviour. In fact, the search for
Fax: +34 91 4974833
b
ICMol. Parque Cientı´fico de la Universidad de Valencia, porosity and catalytic properties has resulted in a specific extension
46980 Paterna, Valencia, Spain. E-mail: carlos.gomez@uv.es of CPs, named metal–organic frame-works (MOFs) or porous
Gonzalo Givaja studied Pilar Amo-Ochoa received a

chemistry at Universidad BSc in Chemistry and a PhD
San Pablo-CEU in Madrid in Inorganic Chemistry from
(1995–2000). Afterwards he Autónoma University of Madrid
finished his MSci in polymeric (Spain). As a postdoctoral
materials at CSIC institute. In researcher she worked on
2006 he finished his PhD thesis Metal-Nucleobases coordina-
on polypyrrolic macrocycles tion chemistry with Prof.
and their late transition metal B. Lippert at Dortmund Univer-
complexes under the guidance sity (Germany). Actually she
of Dr J. B. Love and Prof. Dr has a permanent position in
M. Schröder at the University the Inorganic Department of
of Nottingham. In 2007 he was Autónoma University of Madrid.
awarded a Juan de la Cierva Currently, her research
Gonzalo Givaja postdoctoral grant from the Pilar Amo-Ochoa focuses on coordination poly-
Spanish Ministerio de Educa- mers as possible nanoelectronic
cion at the Universidad Autó- materials. She is the author of B30 papers based on coordina-
noma de Madrid. tion chemistry.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 115–147 115
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coordination polymers (PCPs). These PCPs or MOFs can be

considered as CPs showing large cavities in the structure.
It is well-known that electrical conductivity of classical covalent
polymers has attracted the interest of many researchers in material
science. However, the search of this property in CPs is still very
Scheme 1 The four (left) and two (right) contacts methods for measuring
scarce. Based on recent results, and in part motivated by the high
electrical conductivity. Dimensions l, a and d are the voltage probes
potential of CPs towards nanotechnological applications,1,2 this
distance, the sample width and thickness, respectively.
tendency is being reversed. In addition, the gradual incorporation
of theoretical calculations in CPs seems to be a powerful tool for
I the current, and the proportionality constant, R is the
understanding the experimental measurements and for the rational
resistance), it is straightforward that a measurement of R may
design of new electrically conductive CPs.
simply be done by applying a current (I) and measuring a
Applications in catalysis3 and gas storage4 or gas/molecules
potential (V). Since R depends on geometrical parameters
separation5 are some of the most current active aspects of this
(and, therefore, it is sample-dependent) the magnitude usually
discipline. However, in the near horizon new amazing applications

given is the resistivity (r), which is defined as r = R (A/l),
are being developed connecting this field with nanotechnology.6,7
where A is the cross-sectional area of the conductor (A = a d)
There is no doubt of the technological impact expected for
and l is the distance between the voltage-drop measuring points
coordination polymers within the next coming years, in fact some
(Scheme 1). For historical reasons the resistivity is usually
of them are already used in industrial applications.8
measured in O cm instead of O m, its International System
However, despite the potential implications of high electrical
unit. Besides the resistivity, the other magnitude that is usually
conductivity in CPs in applications such as porous electrodes for
provided is its inverse, called the conductivity, s (=1/r), which
batteries, fuel cells, capacitors, sensors, molecular wires, etc., the
is measured in O1 cm1 = S cm1 (O1 = S = Siemens).
literature on this field is quite disperse and needs to be rationalized
Note that not all conductors obey Ohm’s law. Thus, semi-
in order to understand the data available and to put into a general
conductors and most of the low-dimensional conductors often

perspective their potential. The aim of this review is to summarize
deviate from Ohm’s law, except in a low current range. Further-
the current state-of-the-art of the electrical conductive coordina-
more, even metals only follow Ohm’s law in a limited current
tion polymers and provide a personal point of view towards
or voltage range and, therefore, when resistivity or conductivity
perspectives of these materials and their potential applications.
values are quoted, the current or voltage range in which these
values were obtained has to be specified. Besides the value of
the electrical resistivity at room temperature, it is much more
2. Tools: electrical conductivity measurements. useful to provide its thermal variation since its analysis allows
Conductivity mechanism and low temperature the determination of its electronic nature as will be shown
ground states below.
As stated above, the measurement of the resistance (and,
2.1. Measuring electrical conductivity: methods, problems and
hence, the resistivity) of a sample requires the application of a
solutions
current (I) and the measurement of a voltage drop across the
Electrical conductivity of a material is a measure of its ability sample (V). Unfortunately, these measurements are not so
to conduct electric current under certain conditions (as tempera- simple in most cases since there are different difficulties to be
ture, pressure, applied current,. . .). From the simple Ohm’s solved: the values of the resistivity may vary many orders of
law on conductivity (V = R I; where V is the voltage, magnitude from sample to sample (in fact, the electrical
Carlos J. Gómez-Garcıá was Fe´lix Zamora was born in

born in 1964 in Valladolid 1967 in Cuenca (Spain). In
(Spain). In 1991 he obtained 1994 he obtained the PhD
the PhD in Inorganic Chemistry in Inorganic Chemistry at
at the University of Valencia Universidad Autónoma de
under the supervision of Prof. Madrid. He moved to University
E. Coronado. He moved to the of Dortmund (Germany) to work
University of Rennes in 1993 with Professor B. Lippert.
and to the CRPP in Bordeaux He is currently ‘‘Profesor
(France) to work with Prof. Titular’’ at the Inorganic
P. Delhae`s in 1993–1995. He Chemistry Department at the
is currently a full Professor Universidad Autónoma de
in Inorganic Chemistry and Madrid. From 2004 he focused
works in the Institute of on new nanomaterials with
Carlos J. Gómez-Garcı́a Molecular Science of the Félix Zamora electrical properties based on
University of Valencia. His inorganic systems such as
main research area is focused on the design, synthesis and coordination polymers.
characterization of multifunctional molecular materials presenting
magnetic and electrical properties.
116 Chem. Soc. Rev., 2012, 41, 115–147 This journal is c The Royal Society of Chemistry 2012
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resistivity is the physical magnitude showing the largest range

of values, with differences of ca. 24 orders of magnitude
from silver to quartz). Even more, for a given sample, the
thermal variation may induce changes of several orders of
magnitude in the resistivity. A second problem associated
with the conductivity measurements deals with the effect of
the electrical contacts with the sample. Thus, if the sample
resistivity is very low, the instrument will mainly measure Scheme 2 The four points (left) and the van der Pauw (right) methods
the sample-wire contact resistance. On the contrary, if the used for measuring electrical conductivity in very thin samples.
sample’s resistivity is high, the contact resistance will be
negligible (as observed in most CPs) but if it is very high The other method used for thin samples is the van der Pauw
the experiment may only measure the internal impedance of configuration where the four contacts are glued in the periphery
the voltmeter and leakage currents. An additional problem of the thin plate-like sample (whose thickness is d) approxi-
affecting the conductivity measurements is the lack of homo- mately arranged in the vertex of a square (Scheme 2). The
geneity and the anisotropy of many samples. This aniso- resistivity in this case is calculated using the formula:
tropy may be inherent (low dimensional structures) or due pd Ra þ Rb
to the shape of the sample (single crystals, pressed pellets, r¼ f ðRa =Rb Þ
ln 2 2
thin films,. . .).
All these difficulties have led to the design of different where Ra is the resistance measured along one of the sides of
measuring methods depending on the nature and geometry the square (Ra = VAB/ICD, being VAB the voltage drop across
of the sample and on the magnitude of its conductivity. Thus, A and B when the current passes from C to D) and Rb the
when the resistivity is very low, to avoid the effects of contacts resistance along the other (orthogonal) side (Rb = VAD/IBC,
resistance, the best way is to use the four contacts method being VAD the voltage drop across A and D when the current
(Scheme 1). passes from B to C), the resistance is measured by applying a

This method involves the connection of four parallel in-line current along one side and measuring the V drop across the
contacts to the sample. The two external contacts are used to parallel one. The function f(Ra/Rb) depends on the resistances
apply a current (I+ and I) and the two internal ones are used ratio in a sigmoidal way.9,10 In the ideal case of an isotropic
to measure the voltage drop across the sample (V+ and V). square sample (Ra = Rb = R), the van der Pauw equation
The connection between the thin metallic wires (usually reduces to:
tempered Cu, Ag, Au or Pt wires with diameters of 25–100 mm) pd
r¼ R
and the sample are done with the help of some metallic ln 2
emulsion of fine powders in an organic solvent (silver, gold,
platinum or graphite pastes) or simply by pressing the wires
As already mentioned, an additional problem deals with the
against the sample (if the mechanical resistance of the sample
lack of homogeneity in many samples (either arising from
allows this last method). The resistivity is calculated from the
the shape anisotropy or from the structure of the compound).
cross-sectional area (A = a d) and the distance between the
The shape anisotropy can be well resolved with the van der
internal contacts (l) as r = R (a d/l). The four contacts
Pauw and the four points methods.11 Albeit, the inherent
method is more accurate since it only measures the resistance
anisotropy of the sample requires the use of the Montgomery
of the sample (Rx) but neither the resistance of the wires nor
method or, if possible, the measurement of the resistivity along
that of the contacts as long as the internal impedance of the
different directions or on different faces of the crystals in order
voltmeter is higher than the sample resistance. In contrast, in
to have a complete idea of the electrical anisotropy. The
the two probe method the resistance of the sample and those of
Montgomery method allows the determination of the resistivity
the wires and contacts are added in the measured resistance.
along two different directions in anisotropic samples with a
Since these wire and contact resistances are usually of a few
rectangular prismatic shape (Scheme 3).
Ohms, only for highly conducting samples these resistances
This method requires four contacts in the four corners of
have to be considered. The only (sometimes important)
one of the faces of the prisms (with dimensions a and b). The
advantage of the two-probe method is the smaller limiting
resistivities in the two directions (ra and rb) are calculated with
sample size that can be measured with two contacts (typically
the equations:
above ca. 50 mm vs. ca. 250 mm for the four contacts method).
When the samples are very thin or narrow or are not regular, pffiffiffiffiffiffiffiffiffiffi a Rb pffiffiffiffiffiffiffiffiffiffi
ra rb ¼ f =Ra and ra rb ¼ cRa f 0 b=a
the measurement of the sample dimensions may imply an b
important error, leading to errors in the calculated resistivity.
In these cases, the four-points (different from the four contacts)
and the van der Pauw methods are more convenient. In the first
case, the four in-line contacts are very small equidistant points,
separated by a distance (l) (Scheme 2). Again the two external
contacts are used to apply a current (I) and the two internal
ones to measure the voltage drop (V). The resistivity can be Scheme 3 The Montgomery method used for measuring the electrical
easily calculated as: r = 2p l (V/I). conductivity in anisotropic rectangular prismatic samples.
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where a, b and c are the three dimensions of the prism, (in fact, the classical insulator definition is applied when the
Ra(=V34/I12) and Rb(=V13/I24) are the resistances measured band gap is above 3 eV). When this gap is very small, in a first
along a and b, respectively and f(Rb/Ra) and f 0 (b/a) are approach we can assume that the number of carriers and,
functions that vary exponentially with the ratios Rb/Ra and hence, the conductivity, should show an exponential dependence
b/a, respectively.11 When the sample is a powder the crystal with temperature (s p Ta). This is the case for some
anisotropy is removed but in these cases the conductivity conducting polymers with low doping levels, where values as
has to be measured on a pressed pellet. Unfortunately, in high as 14 can be found for the exponent a.13 In classical
these cases the resistivity is mainly dominated by the inter- semiconductors the thermal dependence of the conductivity
grain boundary contacts, which tend to increase the resistivity follows the Arrhenius law: s(T) = s0 exp(Ea/kT), where
(usually between one and three orders of magnitude) acting as Ea represents the activation energy (corresponding to half of
gaps that block the conductivity or as carrier accumulators. the band gap, Ea = Eg/2) and s0 is a pre-exponential factor.
This behaviour implies that true metallic materials may appear Classical semiconductors are quite common among crystalline
as low band-gap semiconductors or semimetals if they are semiconductors but when dealing with amorphous materials,
measured as pressed pellets. In these cases, the application of conducting polymers or coordination polymers, the conduc-
pressure to form the pellets may also induce irreversible tion mechanism may change from a band model to a localized
transitions that would change the resistivity values and/or one. In this localized model charges move through a so-called
their thermal behaviour. hopping mechanism, which is the term used to describe
Another source of errors in the determination of the exact the ‘‘jump’’ of charges through a phonon-assisted quantum
value of the conductivity is its high sensitivity to the quality of tunnelling mechanism.12,14 The so-called hopping model
the crystals. This problem may lead to significant differences in describes the conductivity with a modified exponential law:
the conductivity measured in different crystals of the same s = s0 exp[(T0/T)a], where the exponent a is related to the
sample. Furthermore, in many molecular superconductors the electronic dimensionality of the sample, a = 1/(1 + d), being
quality of the crystal may determine the critical temperature d the dimensionality. Thus, for one, two and three dimensional
and even the presence or absence of the superconducting systems the a value is 1/2, 1/3 and 1/4, respectively. Note that
transition. Of course, the use of several crystals (at least three for three dimensional systems a = 1/4 and we obtain Mott’s
of four) allows a more precise determination of the value, and law.15 In this expression, s0 and T0 are related to the electronic
the necessary reliability in the observed value. density of the states at the Fermi level, N(F), to the so-called
Finally, it is worth to mention that there are other less common localization length and to the phonons frequency. This variable
problems such as the conduction through humidity layers in the range hopping (VRH) model has been used to explain
sample and the possible reaction of the organic solvent or the conductivity data of many conducting polymers as well as
paste with the sample that may affect the conductivity measure- coordination polymers (the term ‘‘variable’’ arises from the
ments. These and other problems are, fortunately, very scarce fact that the hopping range varies with temperature, since the
and, together with their possible solutions, have already been thermal energy of the electrons and the phonon frequency
discussed in detail.12 change with temperature). Unfortunately in some cases the
data can be fit to different a values (precluding a precise
determination of the electronic dimensionality) or the obtained
2.2. Mechanisms of the electrical conductivity in CPs and low
a value is located between two limiting cases (i.e., when the
dimensional conductors
hopping mechanism appears mainly, but not exclusively, in
Usually resistivity measurements are performed as a function of one or two dimensions).
temperature (from room temperature down to a few K) since the Besides the hopping mechanism, in the case of doped
thermal variation of the conductivity is more informative and conducting polymers and p-conjugated systems there are two
more reliable than the room temperature value. Thus, although additional different mechanisms to explain conductivity:
in a first approach the different electrical behaviours can be polarons/bipolarons and solitons. Polarons are charged carriers
distinguished looking at the room temperature value of the that bear a spin whereas bipolarons are pairs of compensated
conductivity (which is usually in the range 101–105 S cm1 for spins. When the doping level is low, the main carriers are
metals, 1010–101 S cm1 for semiconductors and below ca. polarons in conducting polymers with non-degenerate ground
1010 S cm1 for insulators), the limits between the different states. If the doping increases, then the number of polarons
regimes are not clear.12 The only reliable way to obtain a clear reaches a maximum value and begins to pair in bipolarons.
picture of the electrical behaviour of a compound is to perform This is easily followed by magnetic susceptibility measurements
the thermal variation of the electrical conductivity inside the that show an increase with increasing doping to reach a
Ohmic regime. These measurements show an increase of the maximum followed by a decrease indicative of spin pairing
conductivity (or decrease of the resistivity) with decreasing in bipolarons.16 The second possible mechanism to explain
temperature in metals and the opposite behaviour in semiconductors electrical conductivity in conducting polymers is solitons.
(and insulators). Note that although semiconductors show all a Solitons are localized conformational defects that can easily
thermally activated conductivity (the conductivity increases with move coupled with the lattice vibrations since the energy of the
increasing temperature), the temperature dependence is not the solitons is the same everywhere (in contrast to electrons whose
same in all cases since there are different conduction mechanisms. energy varies from site to site).12,17,18 In one-dimensional
In general, thermally activated semiconductors present conjugated systems at low temperatures this mechanism gives
a small gap between the conduction and valence bands rise to an insulating state since solitons are trapped, given the
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low dimensionality of the lattice. In the case of solitons In one dimensional metals the Fermi surface (that in a
generated by doping (as in the case of slightly doped conducting partially filled band represents the limiting area between the
polymers) the charge born by the solitons interact with occupied and empty wave vector regions) appears as an
the doping counterions, reducing their mobility. When the open surface with a rectangular shape. As the dimensionality
numbers of solitons increase (as in highly doped conducting of the metal increases this rectangle bends more and more
polymers) the solitons form a partially filled band leading to a until it closes to form a cylinder for two-dimensional metals
band-type conductivity. Finally, when charged and neutral and a sphere for three-dimensional metals. When one side
solitons coexist, the trapped charged solitons may hop if the of the Fermi surface can be translated in such a way that
neutral solitons pass near the charged ones. This mechanism is it overlaps with the other side, then the Fermi surface is
called the intersoliton hopping and constitutes a particular said to be nested. The vector describing this translation is
case of hopping conductivity. called the nesting vector. In this situation the metallic state
Other factors that may determine and explain the conducti- is not the stable one30 because the one dimensional metal is
vity in one-dimensional CPs are the localization effects. These expected to suffer a metal insulator transition in the form of a
effects are very important when dealing with very small wires charge density wave (CDW) or a spin density wave (SDW).
(molecular wires in some cases) and are attributed to the These two insulating states are obtained due to the mixing of
presence of unavoidable defects in the lattice.19–21 In these the empty and occupied orbitals near the Fermi surface.
cases, the level of impurities determines the localization of the This mixing of orbitals is important since the energy difference
electrons and if the impurities level is high enough, the electrons between them is small and gives rise to modified empty and
will only present a hopping mechanism between localized states. occupied orbitals. When the temperature is lowered, there
This localization explains the trend towards an insulating state are two possibilities: (1) if the originally occupied orbitals
in strictly one-dimensional conductors when the temperature are now doubly occupied then the metal will present a CDW.
tends to zero, as observed in one dimensional CPs, even if they This state is driven by the lattice vibrations (phonons). (2) If
present, in some cases, weak inter-chain interactions. the on-site electronic repulsion is strong, then the originally
occupied and unoccupied orbitals will bear one electron

each (with anti-parallel spins) in order to minimize the on-site
2.3. Electronic transitions in CPs and low dimensional
electron–electron repulsion. This situation gives rise to a spin
conductors
density wave (SDW). Both states (CDW and SDW) are
Although the main conducting mechanisms in doped polymers insulating because they open a gap at the Fermi level.
and CPs are now well established, there are many systems Other possible electronic transitions observed in conducting
(specially molecular and polymeric) that undergo electronic molecular materials and CPs are the Mott insulators (MI), the
transitions which may be accompanied by structural ones charge disproportionation (CD) or charge ordering (CO), the
when the temperature and/or the pressure are changed. These Wigner solids (a special case of CO) and the spin-gapped (SG)
electronic transitions are usually driven by the relatively strong state (Scheme 4).31
electron–lattice or spin–lattice interactions present in these CD or CO appears when the charge distribution along
systems due to the low dimensionality of the lattice. Among the conducting chain or layer is not uniformly distributed
these transitions the most frequent are the Peierls and spin- (due to the polarising effect of counterions or to structural
Peierls transitions observed in one dimensional systems as KCP dissimilarities, Scheme 4a and d).32–36 The Mott insulators
(K2Pt(CN)4Br0.303.2H2O) and TTF–TCNQ (TTF = tetra- are non-degenerate half-filled band systems where the on-site
thiafulvalene, TCNQ = tetracyanoquinodimethane).22–25 Coulomb repulsion (U) is stronger than the kinetic energy
The Peierls transition can be described as a charge density of the electrons (corresponding to the bandwidth, W).
wave (CDW, see below) that opens a gap at the Fermi level This situation corresponds to those systems where the
giving rise to an insulating state. This CDW is originated by number of electrons is equal to the number of sites (no mixed
a periodic molecular displacement that breaks the regularity of valence exists) and each electron is located in one site to
the chain, resulting in a dimerization of the chain. The driving avoid the on-site repulsions, U (Scheme 4b and 4c for
force for this transition is the gain in electronic energy due to two and one dimensional systems, respectively). In the
the resulting lowering of the Fermi level.18,26 Winger solids besides the on-site Coulomb repulsion (U), the
If the electronic Coulomb repulsion is strong, then the first neighbour Coulomb repulsion (V) also plays an important
localized spins may suffer a magnetic transition to an anti- role when the kinetic energy of the electrons is low (W { U).
ferromagnetic (AF) ground spin state27,28 or a spin-Peierls If these systems present a quarter filled band then the
(SP) transition giving rise to a diamagnetic dimerized system.29 electrons will be localized on alternating sites to minimize
The AF transition occurs when the system presents non- both, U and V (Scheme 4a and d). This special case of CO
negligible inter-chain interactions that increase the electronic (the charge orders in alternating sites) is called the Winger
dimensionality to two or three. The spin-Peierls transition solid. If these systems present a dimerization then the
is observed when the localized spins (that interact along the electron will occupy the bonding molecular orbital formed
chain) suffer a spin pairing (i.e., each couple of equally spaced inside the dimer. This is the so-called dimer-Mott state, where
spins in the chain suffers an antiferromagnetic ordering to a localized and uniform charge distribution is present along
generate paired spins due to a dimerization of the chain). Here the chain (Scheme 4e). The spin-gapped state is a special case
the driving force is the magnetic energy resulting from the of a Mott localized insulator where the spins not only are
antiferromagnetic coupling of the spins in the dimers. localized on adjacent sites but are antiferromagnetically
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Fig. 1 Schematic representation of mixed-valence MX, charge density

wave (CDW) for Pd and Pt complexes (up); and spin density wave
(SDW) for Ni (down).
MX-chains species have been reported so far by applying this

basic principle. The resumed formula of most of them can be
schemed as follows: [ML2][ML2X2]A4 (where M = Ni, Pd and
Scheme 4 Electronic states observed for filled and half-filled band in
Pt, L = alkyl diamine, X = Cl, Br, I and A = Cl, Br, I, ClO4,
one and two dimensional CPs. Electron density is represented as a
violet shadow.
BF4, SO4). Some heterobimetallic compounds have also been
reported in the literature.
coupled to generate a non-magnetic ground state at low According to their valence ordering, two different series of
temperatures. MX complexes are described as depicted in Fig. 1.
A special case of conductivity in CP is the neutral linear-

3.1.1.1. Pd and Pt MX chains. The Pd and Pt MX chain
chain mixed-valence Rh(I/II) semiquinonato/catecholato complex
compounds present a CDW ground state and a lineal structure
[Rh(3,6-dbdiox-4,5-Cl2)(CO)2]n, where an intramolecular
formed by alternating square planar MIIL2 with octahedral
electron transfer between the semiquinonate and catecholate
MIVL2X2 subunits, rendering infinite MIV–X MII chains.
forms of the ligand accounts for the electron delocalization in
The halogen is displaced from the midpoint between metal
the CP.37
centres as a consequence of large electron–phonon coupling.
Finally, it is worth to mention that although very scarce,
These interactions may be tuned by a judicious selection of
there are CPs that present proton conductivity. This conducti-
the in-plane ligands, bridging halides, counterions and metal
vity has been attributed to the presence of water clusters,38
centres. The interchain interactions can also be increased
–OH groups in the coordinated ligands39 and even to one
by introducing H-bond nets that give rise to expanded
dimensional nanoarrays of water molecules,40 although there
dimensionalities.
are no definitive proofs of these mechanisms yet.
Generally, their synthetic procedure encompasses an
equimolecular mixture of both single-valence components,
3. One-dimensional coordination polymers i.e. MII and MIV complexes or controlled oxidation of solutions
containing the MII component.
3.1. Halides bridging metal entities In a series of papers during the 70’s, Interrante and
One extensively studied class of quasi-one-dimensional polymers collaborators studied, among other physical properties, the
encompass species with the abridged formulation MX and electrical conductivity and its pressure dependence of selected
MMX where M is a metal cation, commonly, Ni, Pd or Pt and mixed-valence MX chains,43–45 some of them, like Magnus’
X is a halogen, like Cl, Br or I, acting as a bridge between green salts derivatives, which may be regarded as MX systems,
sequentially spaced metallic centres. These two akin families are out of the scope of this review, but they also conducted
are of great interest, not only for their potential electrical the first electrical characterisation of [Pt(en)2][Pt(en)2X2]X4
transport behaviour, but also for their wide scope of physical (en = ethylenediamine; X = Cl, Br, I) derivatives.43 The
properties. Prime examples are luminescence spectra with large synthetic methods for these compounds had been previously
Stokes shifts,41 large third-order nonlinear optical properties, reported.46–48 At ambient temperature and pressure, the
gigantic third-order optical nonlinear susceptibility42 or conductivity of these sort of complexes along the chain direction
progressive resonance Raman scattering. Along with those, is rather low, o108 S cm1, both in single-crystal and poly-
these materials also exhibit the characteristic features of crystalline samples. Significantly, their conductivity rapidly
quasi-one-dimensional polymers such as spin density wave increases under pressure, with a fully reversible and reproducible
(SDW), charge density wave (CDW), solitons, polarons, and behaviour. A polycrystalline sample of [Pt(en)2][Pt(en)2I2]I4
bipolarons. had an electrical conductivity of almost 1 S cm1 at 160 kbar
whilst that found for [Pt(en)2][Pt(en)2Br2]Br4 analogue was
3.1.1. MX chains. The combination of both dz2 orbitals 103 S cm1, the least conductor species of the series was
coming from the metal centre with the pz orbitals of the halogen [Pt(en)2][Pt(en)2Cl2]Cl4 displaying a 107 S cm1 value. The
bridge renders the theoretically infinite 1D structure ascribed trend I > Br > Cl could be explained in terms of better
for these materials. Over 300 mixed-valence halogen-bridged metal–halogen orbital overlaps. The authors assumed that
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pressure played a role in reducing the geometrical inequivalency

of the metal environments and increasing the intra-
chain metal–halogen orbital overlaps. They also studied the
electrical conductivity of Wolffram’s red and Reilhlen’s green
salts ([Pt(C2H5NH2)4][Pt(C2H5NH2)4Cl2]Cl4 and [Pt(C2H5NH2)4]-
[Pt(C2H5NH2)4Br2]Br4, respectively), but their conductivities were
below the limit of detection even above 140 kbar.
On a latter report, Interrante and Browall continued studying
[Pt(en)2][Pt(en)2X2]X4 systems.43 Four-probe conductivity
measurements were conducted on both single crystals and
pressed pellets. Electrical contacts were made with 2 mm +
platinum wires for the pellet samples and 0.5 mm + gold Fig. 2 Room temperature solid-state structures of: (a) [Pt(en)2]-
coated tungsten wires for single crystals and the wires were [Pt(en)2Cl2](ClO4)4 (displaying disordered bridging chloride positions),
(b) [Pt(en)2][Pt(en)2Br2](ClO4)4 and (c) [Pt(en)2][Pt(en)2I2](ClO4)4.

attached with conducting silver paint. Results of dc conduc-
Counter-ions and hydrogen atoms are omitted for clarity.
tivity measurements at room temperature were reported
as follows: o1011 and 1010 S cm1 for single crystals of
chloride and iodide derivatives, respectively. Afterwards,
[Pt(en)2][Pt(en)2Cl2]Cl4 and [Pt(en)2][Pt(en)2Br2]Br4, respectively,
Kurita et al., in 1987, studied the photoconductivity of the
suitable crystals of the [Pt(en)2][Pt(en)2I2]I4 species could not
iodine derivative and reported an improved electrical conducti-
be grown. Values found for pressed pellet samples were B1015,
vity value of 1.1 108 S cm1.51 Some of the Pd analogues
5 1013 and 1 109 S cm1 for [Pt(en)2][Pt(en)2Cl2]Cl4,
were also electrically characterised by Kida. Thus, [Pd(en)2]-
[Pt(en)2][Pt(en)2Br2]Br4 and [Pt(en)2][Pt(en)2I2]I4, respectively.
[Pd(en)2X2](ClO4)4, (X = Cl and Br) showed conductivities of
In 1981, the research group of Kida reported the electrical
2.0 1012 and 1.2 108 S cm1, respectively, higher than
conductivity of several [ML2][ML2X2]A4 MX chains;49 the
those of the corresponding Pt analogues (Table 1). For instance,

measurements were carried on single crystals using a two-probe
Yamashita reported for a single crystal of [Pd(en)2][Pd(en)2I2]-
method with silver wires contacted with carbon paste along the
(ClO4)4 a conductivity of 5 107 S cm1,52 ca. 300 times higher
needle direction. The complexes [Pt(en)2][Pt(en)2I2](BF4)4 and
than the corresponding Pt derivative (1.6 109 S cm1).
[Pt(en)2][Pt(en)2X2](ClO4)4 (X = Cl, Br, I) exhibited electrical
Kida et al. also reported that [Pt(tn)2][Pt(tn)2X2](ClO4)4
conductivity values of 1.6 109, 2.0 1015, 3.0 1011 and
(tn = triethylenediamine, X = Br and I)49 show similar
1.8 108 S cm1, respectively (Table 1 and Fig. 2). They also
conductivity values (2.0 1014 and 7 107 S cm1, respectively)
found that larger conductivity values could be observed on
to those reported for the en analogues (3.0 1011 and 1.8
single crystal samples.50
108 S cm1, respectively, Table 1).49
As a logical extension of these pioneering works, the Pd
The slow diffusion of I2 vapour into a methanolic solution
analogues were also prepared and studied in the 80’s. Thus, in
of Pt(chnx)2I2 afforded single-crystals of [Pt(chnx)2I]I2 (chnx =
1982, Papavassiliou et al. recorded the electrical conductivity
1R,2R-diaminocyclohexane) as reported by Yamashita and
of pressed pellets of [Pd(en)2][Pd(en)2X2](ClO4)4 (X = Cl and I)
Takaishi in 2006.53 Fig. 3 depicts a view of the solid-state
and found values of 1012 and 2 1012 S cm1 for the
structure evidencing the planar environment of the [Pt(chnx)2]
moieties which are bridged by half-occupied midpoint-displaced
Table 1 Summary of conductivity data reported for one-dimensional
homo and heterometallic MX chains measured with the two probe
bridging iodine, forming linear chains. The authors studied an
method anomalous valence state behaviour caused by the fast fluctua-
tion between PtII I_PtIV and PtIV_I PtII in the double well
Conductivity/S cm1 potential, by using EPR, X-ray diffuse scattering and STM
Compound Pressed pellet Single crystal Ref. images and recorded the electrical conductivity of the complex
[Pt(en)2][Pt(en)2Cl2]Cl4 10 15 a,c
o10 11 a,c
43
using the four-probe method with carbon paste. The observed
107 b value was of the order of 104 S cm1 at room temperature.
13 a,c
[Pt(en)2][Pt(en)2Br2]Br4 5 10 o1010 a,c 43 They also claimed the smallest charge-transfer energy observed
103 b
[Pt(en)2][Pt(en)2I2]I4 109 a,c o108 a 43
1b
[Pt(en)2][Pt(en)2I2](BF4) 1.6 109 a 49
[Pt(en)2][Pt(en)2Cl2](ClO4)4 2.0 1015 a 49
[Pt(en)2][Pt(en)2Br2](ClO4)4 3.0 1011 a 49
[Pt(en)2][Pt(en)2I2](ClO4)4 1.8 108 a 49
[Pd(en)2][Pd(en)2Cl2](ClO4)4 1012 a 2 1012 a 51,53
[Pd(en)2][Pd(en)2Br2](ClO4)4 1.2 108 a 53
[Pd(en)2][Pd(en)2I2](ClO4)4 2 1012 a 5 107 a 54
1.1 108 a 51,52
[Pt(tn)2][Pt(tn)2Br2](ClO4)4 2.0 1014 a 49
[Pt(tn)2][Pt(tn)2I2](ClO4)4 7 107 a 49
[Pt(chxn)2I]I2 104 a 53
Fig. 3 Crystal structures of [Pd(en)2][Pd(en)2Br2](ClO4)4 (a), [Pt(tn)2]-
tn = triethylenediamine, en = ethylenediamine, chxn = 1R,2R-diamino-
[Pt(tn)2Cl2] (b) and [Pt(chnx)2I]I2 (c). All hydrogen atoms along with
cyclohexane. a RT and 1 bar. b RT and 160 kbar. c Four probe method.
counterions have been removed for clarity.
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for this complex compared with all the other halogen-bridged

MX Pt compounds.
3.1.1.2. Ni MX chains. Conversely to Pt and Pd species, due

to the strong electron correlation ascribed to Ni metal centres,
their charge distribution along a MX compound is best
described as infinite NiIII–X–NiIII chains. The strong ligand
field forces the NiIII ion to be in a low spin state (NiIIId7; S = 1/2)
with an unpaired electron occupying the dz2 orbital. In this
situation, the halide sits on the midpoint of neighbouring
Ni pairs conforming a Mott–Hubbard semiconductor with Fig. 4 Single-crystal electrical conductivities of Ni(chxn)2Cl(NO3)2
a SDW ground state. Standard synthetic preparations of and Ni(chxn)2Br(NO3)2. (Data extracted from ref. 57. Reproduced
Ni-based MX chains include previous electrolysis of the with permission of the American Chemical Society.)
divalent discrete compounds in the presence of a pertinent

electrolyte. In this way, many [NiL2][NiL2X2]A4 chains have Fig. 4 shows the electrical conductivity dependence with tempera-
been isolated but only a few selected ones have been the ture for both Ni(chxn)2Cl(NO3)2 and Ni(chxn)2Br(NO3)2.
subject of electrical conductivity studies. Takaishi et al. published in 2008 that the electrolysis
In 1981, Kida et al. also characterised single crystals of the of [Ni(S,S-bn)2]Br2 (S,S-bn = 2S,3S-diaminobutane) in
compound [Ni(en)2][Ni(en)2Cl2](ClO4)4.54 The contacts were anhydrous 1-propanol under a constant 10 mA current yielded
done with silver wires and carbon paste in a two-probe experi- novel [Ni(S,S-bn)2Br]Br2 MX species using tetramethylammonium
ment, the observed electrical conductivity was 1.3 108 S cm1. bromide as the electrolyte.59 Suitable crystals for X-ray diffrac-
A new series of 1D Ni MX chains were reported in 1999 by tion studies were grown over a two-week period. The evalua-
the group of Yamashita,55 both chemical and electrochemical tion of its solid-state structure showed a stronger Ni–Br bond
methods were used for the isolation of [Ni(chxn)2][Ni(chxn)2X2]Y4 than that of the chxn derivative. Thus, in [Ni(S,S-bn)2Br]Br2
species (X = Cl, Br and (Cl/Br), Y = Cl, Br, (Cl/Br), NO3, the Ni Ni contact along the 1D chain is 5.129(1) Å at 120 K,
BF4 and ClO4), as expected, X-ray crystallography confirmed whereas in [Ni(chxn)2Br]Br2 this distance is 5.157(1) Å
a planar N4 donor set for the two in-plane diamine ligands at the same temperature. The electrical conductivity of the
with the Ni(chxn)2 fragments bridged and stacked along the b axis [Ni(S,S-bn)2Br]Br2 complex, measured with the four contact
in all cases. The slow diffusion of Br2 and Cl2 into 2-methoxy- method, showed a quite high room temperature conductivity
propanol solutions of [Ni(chxn)2]Cl2 and [Ni(chxn)2]Br2 led to value of 101 S cm1, decreasing to almost 2.0 104 S cm1
the isolation of Ni(chxn)2Cl2.459Br0.541 and Ni(chxn)2Cl1.28Br1.72, at ca. 133 K (Table 2). Since the X-ray diffraction showed
respectively, X-ray diffraction proved to be a powerful tool the presence of some NiII impurities (due to the synthetic
in order to determine the Cl and Br ratio in both mixed- procedure), the conductivity may be attributed to these Ni(II)
halide compounds. Although their structures were described impurities.58
previously,56 no electrical characterisation experiments were
3.1.2. Heterobimetallic MX chains. When [Pt(en)2X2]X2
undertaken at that moment. NO3, BF4 and ClO4 derivatives
complexes are mixed with Ni(en)2X2 and Pd(en)2X2 species,
were obtained by both chemical and electrochemical methods.
hetero-metal mixed-valence MX compounds result. Firstly
The electrical conductivities of some selected compounds
reported by Papavassiliou60,61 and Kida,62 they have been
were measured on single-crystals using gold wires and carbon
the subject of later electrical conductivity exploration. Thus,
paste with the four-probe method.57 The room temperature
Yamashita et al. compiled their electrical properties studied on
conductivities decreased in the order of Ni(chxn)2Br3 >
single crystals in a later report.52,63 Crystals of Ni(II)–X–Pt(IV)
Ni(chxn)2Cl1.28Br1.72 > Ni(chxn)2Br(NO3)2 > Ni(chxn)2Cl3
species were grown from aqueous solutions containing NaClO4
and presented the following values: 6.92 104, 1.86 105,
whereas those of Pd(II)–X–Pt(IV) were obtained from diluted
2.45 106 and 2.45 107 S cm1, respectively (Table 2).
HClO4 solutions. Conductivity measurements performed
Crystals of Ni(chxn)2Cl2.459Br0.541 were too small to be measured.
along the needle axis for [Pd(en)2][Pt(en)2X2](ClO4)4 showed
room temperature values of 4 1018, 1.4 1015 and
Table 2 Conductivity data reported for single crystals of Ni-based
MX chains at room temperature and 1 bar 4.5 1011 S cm1, for X = Cl, Br and I, respectively.
Those for [Ni(en)2][Pt(en)2X2](ClO4)4 were 3.2 1017 and
Conductivity/S cm1 8.4 1014 S cm1 for X = Cl and Br, respectively (Table 3).
Compounds Two probe Four probe Ref. The experimental data decreased in the order of I > Br > Cl
in both families and values are higher for Ni derivatives than
[Ni(en)2][Ni(en)2Cl2](ClO4)4 1.3 108 54
Ni(chxn)2Br3 6.92 104 55 for Pd. The temperature dependence is shown in Fig. 5.
Ni(chxn)2Cl1.28Br1.72 1.86 105 55 Recent attention has been focused on a novel non-stoichiometrical
Ni(chxn)2Br(NO3)2 2.45 106 55 hetero-metal [Ni1xPdx(chxn)2X]X2 (X = Cl, Br) backbone.
Ni(chxn)2Cl3 2.45 107 57
Yamashita et al. reported in 1999, that combined methanolic
[Ni(S,S-bn)2Br]Br2 101 58
solutions containing different ratios of Ni(chxn)2Br2 and
chxn = 1R,2R-diaminocyclohexane, S,S-bn = 2S,3S-diaminobutane,
Pd(chxn)2Br2 precursors were electrochemically oxidised with
en = ethylenediamine.
tetramethylammonium halides as electrolytes, after several
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Table 3 Summary of conductivity data reported for 1D hetero-

bimetallic MX chains on single crystals with the two probe method
at room temperature and 1 bar
Compounds Conductivity/S cm1 Ref.

18
[Pd(en)2][Pt(en)2Cl2] 4 10 52
[Pd(en)2][Pt(en)2Br2] 1.4 1015 52
[Pd(en)2][Pt(en)2I2] 4.5 1011 52
[Ni(en)2][Pt(en)2Cl2](ClO4)4 3.2 1017 60, 53
[Ni(en)2][Pt(en)2Br2](ClO4)4 8.4 1014 61, 53
en = ethylenediamine.
Fig. 6 Scheme of the 1D polymers synthesised by Castan et al.65–67
are best formulated as [MII(HL)2][MIVX6] and [MII(HL)2]-

[MIV(HL)2X2]X4 (M = Pt and Pd; X = Cl, Br and I), as
depicted in Fig. 6. Their proposed MII X–MIV–X structures

Fig. 5 Electrical conductivity profiles of [Pd(en)2][Pt(en)2Cl2](ClO4)4 are highly reminiscent of that of MX compounds.
(1), [Ni(en)2][Pt(en)2Cl2](ClO4)4 (2), [Pd(en)2][Pt(en)2Br2](ClO4)4 (3), The lack of X-ray diffraction data precluded a concise
[Ni(en)2][Pt(en)2Br2](ClO4)4 (4) and [Pd(en)2][Pt(en)2I2](ClO4)4. determination of the solid state structure of all these complexes;
Measurements performed on single crystals along the needle axis by however, elemental analyses were consistent with the proposed
the two probe method using silver paste. (Data extracted from ref. 53, molecular formulae, while detailed coordination environments
Reproduced with permission of The Chemical Society of Japan.)
were unambiguously resolved by 195Pt NMR spectroscopy for
the Pt analogues and inferred for the Pd ones.
weeks, good quality single crystals of [Ni1xPdx(chxn)2Br]Br2 Powder conductivity measurements were determined on
were formed on H-shaped cells.57 The Ni–Pd ratio was deter- pressed pellets evidencing the semiconductor nature of the
mined by inductively coupled plasma emission spectrometry, samples (Table 4).
X-ray powder patterns of the [Ni1xPdx(chxn)2Br]Br2 complex The electrical properties of the complexes depend on the
revealed an isomorphous phase with the same I222 space group metal centre, on the coordination donor set and on the linking
of the parent starting materials Ni(chxn)2Br2 and Pd(chxn)2Br2, halogen (X). As observed for parent MX chains, the conducti-
hence a halogen-bridged linear structure was assumed for vity increases in the sequence Cl o Br o I. Pd derivatives have
the mixed-metal Ni–Pd species. Interestingly, the PdII–X–PdIV higher values than the Pt ones, and a significant increase, circa
mixed-valence state gradually changed to the unusual two orders of magnitude, is observed on moving from the
PdIII–X–PdIII state on increasing the NiIII content. This obser-
vation indicates that the electron–phonon interaction in
PdII–X–PdIV systems is destabilized by strong electron correla- Table 4 Summary of room temperature conductivity data obtained
tion of the NiIII ion that promotes the change from a CDW on pressed pellets with the two probe method for mixed-valence
heterobimetallic chains with dithiomalonamide
state to a SDW state with a crossover between both at x E 0.7.
IR, Raman, XPS and Auger spectrometry corroborated these Compound M Conductivity/S cm1 Ref.
results. Three years later, in 2002, the same authors informed II IV
[M (HL)2][M Cl6] Pt 3.25 108
67
on the electrical resistance of [Ni1xPdx(chxn)2Br]Br2 and its Pd 7.63 108
dependence with increasing pressure, however, no explicit
II IV
[M (HL)2][M Br6] Pt 3.25 108 66
conductivity results were communicated.64 Pd 7.63 108
[MII(HL)2][MIVBr6] Pt 8.67 108 65
Pd 2.99 107
3.1.3. Other related mixed-valence chains. Other mixed-
II IV
[M (HL)2][M I6] Pt 2.23 107 65
Pd 6.51 107
valence chains have been prepared involving different donor [MII(HL)2][MIV(HL)2Cl2]Cl4 Pt 1.43 106 66
atom sets. Thus, the group of Castan explored the coordination Pd 3.52 106
modes of a variety of thioureas, thioamides, dithiomalon- II IV
[M (HL)2][M (HL)2Br2]Br4 Pt 0.86 105 67
amides and related ligands combined with Pd and Pt cations Pd 1.72 105
[MII(HL)2][MIV(HL)2I2]I4 Pt 7.96 105 65
during the early 80’s.65–67 In this way, they showed that the Pd 9.77 105
dithiomalonamide skeleton (HL) complexes both Pd and Pt to
HL = dithiomalonamide.
form two different series of mixed-valence species which
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the M–M interaction. The resulting geometries have been

called ‘‘paddle-wheel’’ or ‘‘china lantern’’ complexes. The
subsequent oxidative attack at the only open position available
per M atom renders the straightforward formation of the
oxidised MMX2 core (where X = Cl, Br, I, SCN, N3 or
NCO). While there exists a vast number of both MM and
MMX2 dimers, the number of successful bridges to isolate 1D
halogen-bridged MMX infinite chains (X = Cl, Br and I) is
limited to dithiocarboxylates (SCS), diphosphites (POP or
pop) and amidates (RCON2). The abbreviated formulae for
Fig. 7 Structures of the compound Au(DBS)X2 (X = Br and Cl) these chains are: A4[Pt2(pop)4X]nH2O (A = alkali metal,
showing the two possible disordered positions for the halogen atoms: ammonium, alkyl ammonium and alkyl diammonium; X = Cl,
X(1) and X(2). (Data collected from ref. 71 and 72. Reproduced with Br, I; pop = diphosphite = P2O54) and [M2(RCS2)4I]N
permission of The Chemical Society of Japan.) (R = Me, Et, n-Pr, n-Bu and n-Pen for M = Pt; R = Me,
Et, n-Pr and n-Bu for M = Ni).
[MII(HL)2][MIVX6] series to the [MII(HL)2][MIV(HL)2X2]X4 An important consequence of passing from MX to MMX
one. The authors postulated this trend as a consequence of a chains is the gain of internal degrees of freedom from the
better overlap of dz2 orbitals which may lead to a M(III)-like charge–spin–lattice point of view. Thus, now there are new
behaviour. valence ordered states different from those inherent to MX
The coordination chemistry of the dibenzyl sulfide ligand compounds. These states can be summarized as average valence
towards gold was firstly explored by Herrmann by the turn (AV), charge polarisation (CP), charge density wave (CDW)
of the 19th century.68 At that time he isolated an orange and alternate-charge polarisation (ACP) states (Scheme 5).
precipitate with a [Au(DBS)Cl2] (DBS = dibenzyl sulfide) As previously stated, some of the MX compounds are best
formulation. Following this study, Smith reported on the described as CDW systems, in particular those containing Pd
bromide derivative obtained during the study of the addition or Pt, whereas those with Ni are characterised as being
compounds of gold halides with benzyl sulfide.69 It was in 1952 Mott–Hubbard semiconductors. The pop MMX’s are reported
when the first structural assumption for these complexes was to have a CDW ground state (closely related to MX) while
made by Brain and collaborators.70 Their preliminary X-ray SCS have an ACP metal-sublattice dimerisation at low tempera-
study suggested the presence of a 1D Au(III)–Cl Au(I) mixed- ture. Nonetheless, fine tuning of ground state transitions can
valence linear chain in the solid state structure, analogous to be achieved applying pressure or by replacing halogen bridges,
that observed in MX chains. However, the disordered crystal counterions and ligands. In most cases, the nature of the
structure of [Au(DBS)Cl2] species was not resolved until 1988 metallic phases of these chains is attributable to AV or CP
by Takahashi and Tanino,71 who evidenced the infinite electronic structure stabilisation.
Au(III)–Cl Au(I) chain with a positional disorder for the Two main routes can be followed in order to isolate the
bridging chlorine atom, a common feature observed in MX desired mixed-valence species, the first method consist in
chains (Fig. 7). Another remarkable characteristic of the co-crystallising equimolar solutions of the MM and MMX2
structure is the pairing of two 1D chains, the shortest inter- precursors. A second procedure implies partial oxidation
chain contact being 3.32 Å, shorter than the average intra- through halogen addition. In certain cases, as for pop systems,
chain Au–Cl (bridging) distance of 3.41 Å. The structure of the a precipitating agent is also combined in the reaction mixtures.
isomorphous [Au(DBS)Br2] derivative was also reported by Both dta (CH3CS2) and pop derivatives give rise to 1D chains;
the same group three years later (Fig. 7).72 The electrical the dta derivatives are neutral with ligand helical arrangements
conductivities of both chain compounds were measured by wrapping the bimetallic core, while the diphosphite derivatives
Interrante and Bundy in 1977,45 as for most MX chains, these are negatively charged linear chains with almost no twist and
complexes are described as poor conductors at room tempera- the need of a counter-ion.
ture with s o 1010 S cm1 but their conductivities increase
when applying pressure, reaching a broad maximum at ca.
250 kbar with recorded conductivities of 106 and 103 S cm1
for the chlorine and bromine derivatives, respectively. The
measurements were performed using the four-probe method
with 25 mm + gold wires and silver paint. Measurements
under pressure were carried out on a Drickamer apparatus
with diamond compact-tipped pistons.45
3.1.4. MMX chains. When two metal centres are bridged

by four ligands with an appropriate bite angle, such as
amidates or carboxylates, a MM dimeric unit is formed. The
bridging ligands may present different bridging units as OXO
(X = C, S, or P), NCO, NCN, SCS, NCS or PXP (X = O, C).
These three-atom bridges form five membered rings including Scheme 5 Possible electronic states in MMX chains.
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3.1.4.1. Dithioacids with platinum. The first report of the value of ca. 0.23 S cm1 at room temperature, a value similar
electrical properties of Pt2(CH3CS2)4I, published by C. Bellitto to those of other dta family members.79
et al. in 1983, started the quest for metallic conduction On a later report concerning the heat capacity of
involving dta MMX. At room temperature, a compressed Pt2(n-PenCS2)4I, published in 2005, Saito’s group reported
pellet of Pt2(CH3CS2)4I showed a maximum electrical a room temperature conductivity value of 0.84 S cm1 with a
conductivity of 7 103 S cm1.73 Yamashita et al. reported metal–insulator transition at 235 K.81
in 1989 that the electrical conductivity performed on single The obvious difference between these MMX derivatives is
crystals with the two contact method was as high as 2 S cm1 the alkyl chain length, which governs the interchain distances,
at atmospheric pressure and 10 S cm1 at 7 GPa. This increase responsible for the observed physical properties. These properties
with applied pressure is probably due to an increase in the are, at the same time, intimately related to the valence-ordered
energy transfer or a decrease in the band gap and Peirls state. The RT metallic phases of both Pt2(MeCS2)4I and
distortion as pressure rises up.74 They also claimed that thin Pt2(EtCS2)4I are associated with AV states, the crystal struc-
films of the material could be prepared in vacuum with a ture of Pt2(n-PrCS2)4I at RT showed three well differentiated
conductivity of 0.2 S cm1 at room temperature.74 Finally, Pt–I distances as well as alternatively disordered dta ligands.
in 1997, Kitagawa and co-workers provided a new value of When temperature increases, a phase transition occurs at
13 S cm1,75 reinforced by another report of the same group in 359 K, giving rise to a pure AV state for the chain. Similar
1999.76 This discrepancy in the reported values reflects the features are observed for Pt2(n-BuCS2)4I.
already mentioned fact that the exact value of the conductivity DC electrical conductivity measurements carried out on
may be affected by the quality and purity of the single crystals crystals of [Pt2(n-pentylCS2)4I] showed room temperature
(and by the accuracy in the determination of the dimensions of conductivities in the range 0.3–1.4 S cm1.82 Two different
the crystals). The dc electrical conductivity measurements were experiments were used for the conductivity measurements.
carried out along the crystallographic b axis (i.e. through the In the first experiment, the crystals were cooled from 300
Pt–Pt chain using a standard four-probe technique with gold to 100 K and then warmed to 300 K. The cooling run shows
paint and 20 mm + gold wires, between 50 and 380 K. a metallic behaviour with a rounded minimum at around
Metallic behaviour was recorded in the 300–340 K range. 255–270 K, followed by an abrupt increase at ca. 200 K
Increasing the number of carbon atoms in the lateral chain (Fig. 8b). The thermally activated regime follows the 1D
of the dithiocarboxylic acid may tune the observed Pt–Pt and variable range hopping model (s = s0* exp[(T0/T)1/2]),
Pt–I distances. It can be anticipated that bulkier aliphatic 1D-VRH, used to explain conductivity in many conducting
chains will impose a demanding steric repulsive interaction polymers. This fact suggests that the conductivity in
resulting in elongated Pt–Pt contacts. In 2001, Mitsumi [Pt2(n-pentylCS2)4I] is mainly one-dimensional, as expected
et al. reported the synthesis and characterisation of novel from its linear structure. However, this model does not
Pt2(EtCS2)4I species.77 Single crystal X-ray analyses confirmed reproduce the conductivity in the intermediate temperature
the 1D nature of the structure. The Pt–Pt (2.684(1) Å) and Pt–I range 225 o T o 255 K, which suggests the presence of an
(average 2.980 Å) distances measured at 293 K were slightly
longer than those observed for the parent Pt2(CH3CS2)4I
compound (Pt–Pt 2.677(2) Å, Pt–I (average) 2.978 Å). Electrical
transport measurements concluded that the polymer was a
metallic conductor showing an electrical conductivity between
5 and 30 S cm1 at room temperature (again the values differ
for different crystals). The results were tested in several single
crystals using the four-probe technique with gold paint contacts
and 25 mm + gold wires. The temperature was varied from
80 to 400 K and a metallic-semiconductor transition was
observed at 205 K.77
Several MMX chains were reported later in the following
year by the same authors.78,79 In these compounds the dimetallic
Pt–Pt units were built with n-PrCS2H and n-BuCS2H dithio-
acid ligands to form the corresponding Pt2(n-PrCS2)4I and
Pt2(n-BuCS2)4I chain polymers. These compounds were examined
with classical inorganic techniques and further characterised
through four-probe electrical transport measurement on single
crystals. The n-BuCS2 derivative displayed at room tempera-
ture an electrical conductivity in the range 17–83 S cm1 and a
phase transition at 325 K. The same year Nakazawa and
Fig. 8 (a) A single polymer chain of [Pt2(n-pentylCS2)4I]. (b) Thermal
co-workers published a heat capacity study of the complex and variation of the electrical resistivity of [Pt2(n-pentylCS2)4I]. The
reported an approximate electrical conductivity of 30 S cm1 dashed line shows the behaviour of a non-heated sample. The inset
(in the range already observed by Mitsumi and Toriumi) with shows the derivative of the resistivity vs. temperature around the
weak temperature dependence.80 In 2002, Mitsumi et al. RT-HT transition. (From ref. 82. Reproduced with permission of
reported that Pt2(n-PrCS2)4I showed an electrical conductivity Wiley-VCH.)
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Table 5 Summary of conductivity data obtained for [Pt2(dta)4I] The last MMX chain incorporating dta ligands came out in
(dta = alkyldithiocarboxylates) chains in single crystals with four 2009.83 The group of Saito conducted a study concerning the
contacts
heat capacity, absorption spectrum, spin susceptibility and
Compounds Conductivity/S cm1 Ref. electrical conductivity of Pt2(n-HexCS2)4I. The four-probe
a,c b,c method revealed a value of 2 103 S cm1 at room tempera-
Pt2(CH3CS2)4I 2 /10 73–75
7 103 a,c,d/13a ture, a value slightly lower than those typically observed for Pt
Pt2(EtCS2)4I 5–30a 77 MMX derivatives (Table 5).
Pt2(n-PrCS2)4I 0.23a 78 The data collected in Table 5 summarized the excellent
Pt2(n-BuCS2)4I 17–83a 79
Pt2(n-PenCS2)4I 0.3–1.4a 81, 82 electrical conductive properties found in these polymers.
Pt2(n-HexCS2)4I 2 103 a 83
a
RT and 1 bar. b RT and 7 GPa. c Two probe method. d
Pressed pellet. 3.1.4.2. Dithioacids with nickel. In addition to Pt2(CH3CS2)4I,
Bellitto et al. also reported the synthetic procedure, isolation and
characterisation of Ni2(CH3CS2)4I back in 1985.84 Its solid-state
intermediate regime between the metallic and semiconducting

structure consisted of linear Ni2(CH3CS2)4–I–Ni2(CH3CS2)4–I–
regimes. In the intermediate regime, the coexistence of metallic
chains stacked along the b crystallographic axis. They also
and semiconducting regimes may be attributed to a progressive
measured an electrical conductivity of 5 106 S cm1 for what
distortion of the Pt–I distance along the chain.
at that time was the first example of a conductive nickel mixed-
In the second experiment, the crystals were heated from 300
valence 1D-chain. The electrical measurements were made on
to 400 K and then cooled to 100 K, followed by a final heating
pressed pellets of the compound using the two-probe technique.
scan from 100 to 400 K (Fig. 8b). An irreversible RT-HT
Later electrical conductivity measurements performed by
transition was confirmed. The heated crystals also show an
Yamashita’s group on single crystals with the four-probe method
abrupt metal–insulator transition at ca. 200 K and after this
gave an improved conductivity of 2.5 102 S cm1.85
M–I transition, the crystals again suffered important micro-
While continuous reports concerning Pt2(RCS2)4I have

cracks and showed a resistivity 103–104 times higher than that
appeared in the literature during the last few decades, the
observed before the transition. The structural changes that
number of papers related to the nickel derivatives, Ni2(RCS2)4I,
cause the electrical behaviour observed for [Pt2(n-pentylCS2)4I]
are much more limited. In fact, only very recently, in 2009, the
were confirmed by X-ray diffraction analyses (Fig. 8). Studies
NiMMX family has been enlarged by Mitsumi et al. who
on crystals of [Pt2(n-pentylCS2)4I] carried out at three tempera-
successfully isolated and electrically characterised the R = Et,
tures (100 (LT), 298 (RT) and 350 (HT) K) showed the existence
n-Pr and n-Bu derivatives in the series Ni2(RCS2)4I.86 The
of three different phases for [Pt2(n-pentylCS2)4I].
reported room temperature electrical conductivity values are:
1.6 103, 7.6 104 and 6.0 104 S cm1 for R = Et, n-Pr
Table 6 Conductivity data reported for chains of [Ni2(dta)4I]
and n-Bu, respectively (Table 6). The measurements were
(dta = alkyldithiocarboxylates) chains on single crystals with four
contacts performed with the four-probe method on various single crystals
using gold paint and 20 mm + gold wires. The compounds
Compounds Conductivity/S cm1 Ref. were synthesised in low yield (3–7%) by exposing solutions of
2 a
Ni2(CH3CS2)4I 2.5 10 84, 85 the corresponding MM dimer to iodine vapours. These solutions
5 106 a,b yielded black single crystals whose structures show neutral 1D
Ni2(EtCS2)4I 1.6 103 a 86
chains built up with repeating Ni–Ni–I units (Fig. 9).
Ni2(n-PrCS2)4I 7.6 104 a 86
Ni2(n-BuCS2)4I 6.0 104 a 86 Both Ni2(MeCS2)4I and Ni2(EtCS2)4I derivatives present a
a b CP state at room temperature. In the n-Pr derivative, Ni2(n-PrCS2)4I,
RT and 1 bar. Pressed pellet and two probe.
there are three significantly different Ni–I distances, the valence
Fig. 9 Room temperature solid-state structure and significant distances of Ni2(EtCS2)4I (a), Ni2(n-PrCS2)4I (b) and Ni2(n-BuCS2)4I (c). All
hydrogen atoms not displayed for clarity. Disordered ligand chain position shown.
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order can be regarded as –I Ni3+–Ni2+–I Ni2.5+–Ni2.5+– Table 7 Summary of conductivity data reported on K4[Pt2(pop)4X]
I Ni2+–Ni3+–I , rendering an approximate AV ground 3H2O chains, (X = Br, I) with the two probe method
state at RT, attributed to the entropy reservoir of the ligand Compounds Conductivity/S cm1 Ref.
alkyl chains. A similar behaviour was observed in Ni2(n-BuCS2)4I 4 3 a,c
chains. The four Ni2(dta)4I compounds show semiconducting K4[Pt2(pop)4Br]3H2O 5 10 –1 10 88
K4[Pt2(pop)4I]3H2O 2.8 104 a,b 88
behaviour as well as an intense sharp absorption band at a b
RT and 1 bar. Pressed pellet. c Single crystal pop = pyrophosphates.
5400 cm1, which is assigned to a Mott-Hubbard gap due to a
relatively large on-site Coulomb repulsion energy (U) of the
nickel atoms. 3.1.4.4. Other MMX systems. Whilst not formally considered
Tables 5 and 6 collect the conductivity data of the MMX as MMX in the literature, there exist a large number of
chains M2(dta)4I (M = Ni and Pt) and show impor- compounds having this formulation. Kawamura et al. reported
tant differences of ca. 3 orders of magnitude in the electrical the first examples of halide-bridged paddle-wheel chains enclosing
conductivity values between analogous compounds with different a Rh25+ core with wrapping acetamide (CH3CONH2 = acam)
metals. DFT calculations87 suggest that these differences could ligands in 2000.89
be associated to the greater localization of the 3d states of Crystals of [Rh2(acam)4Cl]n7nH2O and [Rh2(acam)4Br]n
Ni compared to the 5d states of Pt and to the electron– were isolated by reacting the Rh25+ precursor with sodium
lattice dominant interactions in Pt2(dta)4I compared to Ni2(dta)4I, halides. Their structures comprise zig-zag chains of repeating
where the solid state properties are governed by the strong (–Rh–Rh–X–)n units assisted via hydrogen-bond formation
electron correlation of the Ni atoms.86 between amidato-NH donors and amidato-O acceptors of
adjacent units for the bromide chain and between amidato-O
and interstitial water molecules for the chloride derivative as
3.1.4.3. Platinum with pop. The A4[Pt2(pop)4X]nH2O depicted in Fig. 11. Pressed pellets of both compounds showed
(A = alkali metal, ammonium, alkyl ammonium and alkyl a conductivity value below 2 107 S cm1 at room tempera-
diammonium; pop = P2O5H22; n = 0, 2 and 3; and X = Cl, ture. One year after, on a subsequent report, the iodide
Br, I) family contains more than 50 structurally characterised derivative (Fig. 12) was isolated and crystallographically and
linear chains, all of them described as being insulators and electrically characterised.90 This derivative was found to be
presenting AV, CP or CDW valence states, in contrast with the
dta family which, in some cases, can stabilise an ACP phase
related to their metallic electrical transport properties.
In 1983, the group of Gray prepared the first example of
partially oxidised K4[Pt2(pop)4X] linear chains88 and reported
the synthesis of K4[Pt2(pop)4Cl], K4[Pt2(pop)4Br]3H2O and
K4[Pt2(pop)4I], the X-ray single-crystal structure of the bromine
derivative, K4[Pt2(pop)4Br]3H2O and the electrical properties
of the bromine and iodine derivatives, K4[Pt2(pop)4Br]3H2O
and K4[Pt2(pop)4I] (Fig. 10). Conductivity measurements carried
out on several single crystals of K4[Pt2(pop)4Br]3H2O with
the standard two-probe method revealed at room temperature
conductivity values in the range 5 104–1 103 S cm1.
The small crystal size of the iodine derivative prevented a
detailed examination of the solid-state structure and subsequent
measurement of its electrical behaviour; however a compressed
pellet showed a value of 2.8 104 S cm1 at 298 K. In 1986,
Clark and co-workers reported the crystal structure of the
chlorine derivative, K4[Pt2(pop)4Cl], and showed that it is consti- Fig. 11 Crystal structure of [Rh2(acam)4Cl]n7nH2O (up) and
[Rh2(acam)4Br] (down) with partial numbering scheme. Hydrogen
tuted by Pt2+–Pt3+–Cl polarised repeating units.
atoms not shown and only selected water solvent molecules are
The data collected in Table 7 show the significant (3–5 orders
displayed. Short range contacts depicted as red dotted lines.
of magnitude) decrease in conductivity between K4[Pt2(pop)4X]
and their Pt2(dta)4I analogues (Table 5).
Fig. 10 A fragment of the molecular structure of K4[Pt2(pop)4I] species,

counterions and cocrystallised water molecules are not displayed for the Fig. 12 Solid-state structure of [Rh2(acam)4I]n with atom label scheme.
sake of clarity. Short interdimer amide contacts shown as red dotted lines.
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Table 8 Conductivity data on pressed pellets with the two probe method reported on several MMX chains

7 a
[Rh2(acam)4Cl]n7nH2O 2 10 89
[Rh2(acam)4Br]n 2 107 a 90
[Rh2(acam)4I]n 2 107 a 90
[Rh2(acam)4(H2O)2][Rh2(acam)4{(m-Cl)2PtCl2}]2H2O 107 a 91
[Rh2(acam)4(H2O)2][Rh2(acam)4{(m-Cl)2PdCl2}]2H2O 107 a 91
[–Pt–Rh–Pt4–Rh–Pt–Cl–]n 3.52 106 a,b 92
{[PPh4]2Te2Ru4(CO)10Cu4Br2Cl2)THF}N 5 102 a 93
a b
acam = CH3CONH2. RT and 1 bar. Four probe, single crystal.
[Rh2(acam)4(H2O)2][Rh2(acam)4{(m-Cl)2PdCl(H2O)}]H2O, were
obtained (Fig. 13). All of them present infinite (–Rh–Rh–Cl–M–Cl–)n
repeating units, forming zig-zag chains in the two first cases

and helical in the third one (Fig. 13).
The observed room temperature conductivity values measured
on pressed pellets of the two derivatives [Rh2(acam)4(H2O)2]-
[Rh2(acam)4{(m-Cl)2MCl2}]2H2O (M = Pt and Pd) were
around 107 S cm1. These values are similar to those observed
for related Rh25+ chains.
Besides these 1D structures, paddle-wheel complexes
constructed with Rh25+ cores and acetamide ligands may also
display several coordination modes when bridged by halides,

rendering 2D and 3D dimensional structures. These will be
discussed in the following sections.
Closely related to MMX polymers, there exists a short
number of extended linear metal atom chains bridged by halogen
linkers [MnX]N, however, limited information is reported in
terms of their electrical transport properties. A good example
Fig. 13 Crystal structure of different infinite (–Rh–Rh–Cl–M–Cl–)n of this series was reported in 2005 by Matsumoto’s group, who
chains M = Pd (top), M = Pt (center) and M = Pd (bottom). succeeded in the isolation of a mixed-metal mixed-valence
quasi 1D system shown in Fig. 14. Its solid-state structure
almost isostructural with the dehydrated chlorine chain, revealed a [Pt6Rh2]19+ repeating octameric core bridged by two-
crystallising in the same C2/c space group with similar cell coordinated chloride ions rendering a [–Pt–Rh–Pt4–Rh–Pt–Cl–]n
parameters. The observed conductivity of a pressed pellet was infinite chain.92,94 The octamer can be viewed as being formed by
107 S cm1 (Table 8). four dimeric units: two inner Pt–Pt dimers (Pt1–Pt2 and Pt3–Pt4)
Although the halide bridging two paddle-wheel complex has and two outer Pt–Rh dimers (Pt5–Rh1 and Pt6–Rh2), all of
proven to be a successful strategy, it is not the only one. Thus, them doubly bridged by pivalamidate ligands that warrant
another approach for the formation of linear chains may both close metal–metal contacts and interdimeric hydrogen
include additional metal halide cores as linkers. In this regard, bond formation between amide oxygen and amine groups
Ebihara et al. have recently published the compounds formed along the chain. Since two ammonia groups complete the
by reaction of K2MCl4 (M = Pd, Pt) with the cationic complex coordination requirements of the Pt cations, two monodentate
Rh2(acam)4+.91 Thus, the reaction between [Rh2(acam)4(H2O)2]- chloride ligands complete the Rh1 and Rh2 environments and
ClO4 and K2PtCl4 yielded the chain compound formulated as balance the charge.
[Rh2(acam)4(H2O)2][Rh2(acam)4{(m-Cl)2PtCl2}]2H2O, whereas The electrical conductivity measured by the four-contacts
when K2PdCl4 was used, two different compounds, formulated method shows a semiconducting behaviour with a room
as [Rh2(acam)4(H2O)2][Rh2(acam)4{(m-Cl)2PdCl2}]2H2O and temperature conductivity of 3.52 106 S cm1 along the
Fig. 14 Crystal structure of the octanuclear quasi 1D chain isolated by Matsumoto’s group.
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Fig. 15 Solid-state structure of {[PPh4]2Te2Ru4(CO)10Cu4Br2Cl2)

THF}N, PPh4 counterions and co-crystallised THF solvent molecules
are not displayed for clarity.
perpendicular chain direction, crystal thin plate morpho-

logy precluded conductivity measurements along the chain
direction.
During their investigation on Te2Rh4 cluster formation,
Shieh et al. succeeded in the isolation and characterisation of
a number of discrete Te–Ru–Cu carbonyl complexes, including
the first Cu(Br)CuCl-bridged Te2Rh4 octahedral cluster chain
polymer: {[PPh4]2Te2Ru4(CO)10(Cu4Br2Cl2)THF}N. The electrical
conductivity measurements of this compound showed a room Fig. 16 One-dimensional polymeric structures of cyanopyridine
temperature conductivity of 1–5 102 S cm1 and a semi- polymers with [Cu(pyridine-3,4-dicarbonitrile)2(SCN)]n (top) and
conducting behaviour.93 [Ag(pyridine-3,4-dicarbonitrile)2(NO3)]n (bottom)). Close non-bonding
This polymeric {[PPh4]2Te2Ru4(CO)10Cu4Br2Cl2)THF}N interaction for [Ag(pyridine-3,4-dicarbonitrile)2(NO3)]n displayed as red
chain was prepared by reaction between K2TeO3 and Ru3(CO)12 dotted lines.
followed by treatment with PPh4Br and CuCl. Its crystal structure
(Fig. 15) can be described as formed by Te2Ru4 octahedral
Table 9 Summary of conductivity data reported at room temperature
units, each Ru centre is coordinated to two terminal CO and 1 bar on 1D-CPs with cyanopyridines as linkers
groups, two Cu2Br cores and a bridging CO group connecting
opposite pairs of Ru2 units. There is also a short interaction of Compounds Conductivity/S cm1 Ref.
one Cu centre with an apical Te atom. These repetitive units [Ag(3-cyanopyridine)2(NO3)]n 1011 d 95
are further connected by chloride bridges forming an anionic [Ag(pyridine-3,4-dicarbonitrile)2(NO3)]n 7.3 106 d 95
chain, whose charge is balanced with PPh4+ counterions [Cu(4-cyanopyridine)2(SCN)]n 1013 d 95
[Cu(pyridine-3,4-dicarbonitrile)2(SCN)]n 4.3 105 d 95
running along the b axis. A solvated THF molecule is enclosed [{Cu(TANC)}F0.5]n 50a,e 96
in the asymmetric unit cell. 0.91b,e
6.90 103 c,e
3.2. Cyanopyridines as linkers TANC = 5,6,11,12-tetraazanaphthacene. a Along a axis. b Along
b axis. c Along c axis at 303–393 K. d Pressed pellets and two probe.
Cyanopyridine ligands offer two different donor nitrogen sites e
Single crystal and four probe.
located at their ends. These nitrogen donor atoms differ in
steric requirements and basic character. Thus the cyano
nitrogen atom is a weaker donor than the pyridine one. Indeed although with a different thermal reversibility. Thus, on one
this is the reason why organic molecules, and counteranions hand, the Ag(I) polymer shows a thermal reversible behaviour
can connect to the metal centre easier than the cyano nitrogen, and its conductivity increases by a factor of 2 (from 7.37 106
resulting in the formation of complexes in which the n-cyano- to 15.1 106 S cm1) as the temperature increases from
pyridines act as monodentate ligands and the cyano groups are 298 K to 358 K. On the other hand, the Cu(I) polymer shows
not coordinated to the metal. an irreversible thermal dependence and the conductivity increases
In a work carried out by Henderson and co-workers,95 only by 25% (from 4.29 105 to 5.39 105 S cm1) when
several one dimensional coordination polymers of n-cyano- the temperature is varied in the same range (298–348 K). This
pyridines (n = 3, 4) and pyridine-3,4-dicarbonitrile with Ag(I) difference can be explained according to their structures. Thus,
and Cu(I) have been explored. In some of the polymers in [Ag(pyridine-3,4-dicarbonitrile)2(NO3)]n the one dimensional
reported n-cyanopyridine and pyridine-3,4-dicarbonitrile ligands chain shows short and stable Ag–O bonds that form a stable
coordinated in a monodentate fashion while NO3 and SCN and effective conjugated system in the measured temperature
bridge the metal centres (Fig. 16). range. The authors explain the difference claiming that in
The electrical characterisation carried out with the two-probe [Cu(pyridine-3,4-dicarbonitrile)2(SCN)]n, the Cu(I) in the
method on pressed pellets (Table 9) shows that the coordina- crystal is reduced at high temperature by the SCN resulting
tion polymers [Cu(4-cyanopyridine)2(SCN)]n and [Ag(3-cyano- in Cu0 doped semiconducting behaviour. It should be also
pyridine)2(NO3)]n are insulators in the whole range of mentioned that none of the two polymers shows metal–metal
temperature (290–350 K). bonding in their structures.
[Ag(pyridine-3,4-dicarbonitrile)2(NO3)]n and [Cu(pyridine- The 1D-coordination polymer [{Cu(TANC)}F0.5]n was obtained
3,4-dicarbonitrile)2(SCN)]n show a semiconductor behaviour by reaction of 5,6,11,12-tetraazanaphthacene (TANC) and
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Fig. 17 One dimensional structure of [{Cu(TANC)}F0.5]n with alter-

nating linkages between Cu(I) ions and TANC. Only relevant H atoms
depicted for clarity.
Fig. 18 Fragments of the polymeric chains of compounds
[Ni(6-MP)22H2O]n(left) and [Ni(6-ThioG)22H2O]n (right).
[Cu(MeCN)4]BF4 in MeOH/MeCN. The presence of half an
equivalent of non-stoichiometric F ions was determined by
X-ray photoelectron spectroscopy and quantitative chemical Table 10 Conductivity data reported at room temperature and 1 bar
analysis of F ions. These F ions are generated by the on single crystals with the two probe method on 1D-CPs containing
nucleobases
dissociation of BF4 anions in the reaction mixture (Fig. 17).96
Conductivity measurements for this complex, performed Compounds Conductivity/S cm1 Ref.
with the four-probe method, showed a high room temperature 5
[Ni(6-MP)22H2O]n 1.10 10 101
conductivity of 50 S cm1 along the a axis. This value [Ni(6-ThioG)22H2O]n 1.34 104 101
decreases rapidly to 106 S cm1 at 10 K showing a semi-
6-MP = 6-mercaptopurinate, 6-ThioG = 6-thioguaninate.
conducting behaviour. Conductivity measurements performed
in different crystal directions showed a high anisotropy with
room temperature values of 50, 0.91 and 6.90 103 S cm1 Thus, direct hydrothermal reactions between 6-mercaptopurine
along the a, b and c directions, respectively. These results are (6-MPH) and the analogous 6-thioguanine (6-ThioGH) with
explained based on the disordered F ions, which affect the NiSO46H2O gave [Ni(6-MP)22H2O]n and [Ni(6-ThioG)22H2O]n
stacking of the TANC columns since the particular crystal (Fig. 18).
structure of this compound shows alternating layers of F The structures of these coordination polymers are rather
ions that disturb the conductivity through the c axis. This similar to that with Cd(II) and consist of one-dimensional
means that the crystal behaves as a quasi-1D molecular semi- chains in which the deprotonated nucleobases act as the
conductor with a relatively good conductivity in the ab plane bridging ligands connecting the metal ions with short M–M
and a maximum conductivity along the a axis, corresponding distances (3.677 and 3.646 Å). Two probe DC electrical
to the 1D stacking of the TANC ligands.96 Table 9 collects conductivity measurements at 300 K show ohmic behaviour,
conductivity data reported on these coordination polymers. with conductivity values of 1.10 105 and 1.34 104 S cm1,
for [Ni(6-MP)22H2O]n and [Ni(6-ThioG)22H2O]n, respec-
3.3. Systems containing nucleobases
tively (Table 10).101 The small differences found in these
The design and construction of coordination polymers measurements were rationalized with the help of additional
containing nucleobases as either terminal or bridging ligands DFT calculations. The main difference is that the lattice
is of interest due to their abilities to act as functional materials constant obtained by GGA-DFT calculations is 2.2% smaller
given their particular electrical, magnetic, catalytic and non- than that obtained by X-ray analysis. This leads to an increase
linear optical properties. Three-dimensional coordination of B14% in the HOMO–LUMO gap (0.77 eV for the
polymers may also show applications in molecular storage (gases, X-ray structure) with respect to the value obtained for the
anionic exchange, etc.) and/or molecular separation. The theoretical geometry. The calculated electronic structure of
formation of polymers based on biologically relevant ligands, [Ni(6-ThioG)22H2O]n presents similar electronic properties to
such as nucleobases, may provide additional applications in those observed for [Ni(6-MP)22H2O]n, with a calculated
biological fields. For instance, some of these structures could HOMO–LUMO gap of 0.69 eV. By comparing the band
be used as models of specific forms of DNA (e.g. M-DNA, structures of [Ni(6-MP)22H2O]n and [Ni(6-ThioG)22H2O]n,
G4,. . ..).97 It is surprising that there are relatively little number it is observed that the amino group, present in the
of polymeric structures based only on bridging nucleobases, [Ni(6-ThioG)22H2O]n, mainly introduces modifications in
despite the number of available coordination positions. the deep level states lying at about 1.25 eV from the Fermi
Recently, one of these examples has attracted particular level, and below. The lower gap observed for [Ni(6-ThioG)22H2O]n,
attention since its structure resembles that initially suggested when compared with [Ni(6-MP)22H2O]n, is due to the fact
for M-DNA (a novel type of DNA).98 The initial studies were that the former presents a smaller lattice constant (3.65 Å)
carried out on the [Cd(6-MP)22H2O]n (6-MP = 6-mercapto- than the latter (3.68 Å). By using the value we obtained for the
purinato) polymer showing an insulating behaviour which difference in band gaps between the two coordination polymers,
could be explained as a consequence of the large HOMO–LUMO we have estimated that polymer [Ni(6-ThioG)22H2O]n should
band gap.99 Subsequent DFT calculations performed with the have about 20 times more thermally activated intrinsic carriers,
aim of designing suitable electrical conductive [M(6-MP)2]n at room temperature, than [Ni(6-MP)22H2O]n which is consistent
(M = transition metal, 6-MP = 6-mercaptopurinato) one- with the experimental conductivity measurements.
dimensional coordination polymers pointed out that several Therefore, it seems that theoretical calculations are a suitable
metal ions such as Ni(II) could provide suitable materials.100 tool to understand experimental measurements but, even
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more important, to design coordination polymers with the

desired property.
3.4. Sulfur ligands as linkers

The field of molecular organic conductors has been widely
studied in recent years, focusing mainly on the synthesis of
charge transfer complexes based on tetrathiafulvalene
(TTF).102 Compounds of this type with intermolecular S S
contacts have shown metallic conductivity and, in some few
cases, even superconductivity.103 These results have encouraged
researchers to select ligands with similar structural features
(Fig. 19) and extend the electrical conductivity studies towards Fig. 20 Suggested structures for the two types of heterobimetallic
coordination compounds and coordination polymers. coordination polymers with i-mnt2 ligands.
TTF derivatives are p-electroactive compounds with chelating
sites such as the organylthio groups, which could potentially 4,5-dimercapto-1,3-dithiole-2-thione (dmit2)106 and 1-ethoxy-
further enhance the bonding and electronic interaction between carbonyl-1-cyanoethylene-2,2-dithiolate (ecda2)107,108 have
the metal centre and the organic ligands. These organosulfur been prepared by reaction of M2M 0 L2 (L = mnt2, i-mnt2,
groups can act as linkers between metallic centres to form ecda2, dmit2; M = Na and K, and M 0 = Cu(II), Ni(II), Au(I))
charge transfer complexes that could act as Synth. Met. or with a solution of different metallic salts (Ag(I), Pd(II), Cd(II),
semiconductors. The physical properties of these compounds Pb(II), Hg(II), Cu(I) and Au(I)) in the appropriate molar ratio.
not only depend on the specific molecular properties of the Their structural characterisation have been carried out by
individual components, metal ions and sulfur ligands, but are spectroscopic techniques suggesting the formation of one-
also strongly influenced by the arrangement of interactions dimensional coordination polymers in which the metal entities
within the crystal lattice.104 are connected by the sulfur atoms of the organic ligands to
The coordination of TTF derivatives to metal ions provides generate heterobimetallic layered polymeric structures
a wide variety of conductive complexes and coordination (Fig. 20). These structures extend the electron delocalization
polymers. These CPs exhibit a broad panel of electrical properties beyond the MS2 group and hence exhibit interesting conducti-
due to the existence of a coordination polymeric network that vity in its complexes (Table 11).
can be achieved through the coordination of metal ions and/or The electrical characterisation showed that the conductivity
through the S S contacts. In the following lines we will of these materials increases upon heating and decreases
describe some examples of electrical conductive coordination upon cooling showing a typical semiconductor behaviour
polymers with this kind of ligands. (Table 11).
A series of heterobimetallic compounds with maleonitrile- In the case of [M 0 2Ni(dmit)2]n the polymeric structures
dithiolate (mnt2),105 isomaleonitriledithiolate (i-mnt2),105 present additional metal ions that interconnect the [M0 Ni(dmit)2]
(M 0 = Cu, Ag and Au) linear chains through S–M–S bonds
(Fig. 21).106 The high value of 1.6 S cm1 observed for the
complex [Au2Ni(dmit)2]n (Table 11) is remarkable. The
authors attributed this value to the oxidation state observed
in the [Ni(dmit)2] units.106
The iodine doping of the [MCu(i-mit)2] derivatives (M = AgI,
CdII, HgII and PbII) seems to be an effective strategy for the
synthesis of electrically conductive compounds. A remark-
able increase in the conductivity, i.e. 106–105 S cm1 for
the iodine-doped coordination polymers as compared to
109–106 S cm1 for the respective undoped compounds, is
observed.105 The authors state that this could be due to stronger
intermolecular S S stack formation as well as partial oxidation–
reduction (mixed valence state) of the metal ions.
In a similar approach, N. Singh and Prasad have synthesized
several heterobimetallic coordination polymers (1D and 2D)
by reaction of two equivalents of the corresponding mixed
metal salts with one equivalent of benzothiazole-2-thiolate
Fig. 19 Structures of some representative tetrathiafulvalene ligands:
2,5-bis(4 0 ,5 0 -bis(methylthio)-1 0 ,3 0 -dithiol-2 0 -ylidene)-1,3,4,6-tetrathia-
(bzta) or diethylthiocarbamate (Et2dtc) and one equivalent
pentalene (TTM-TTP), maleonitriledithiolate (mnt2), isomaleonitrile- of chalcogenocyanates (XCN) (X = S or Se).113 In this case,
dithiolate (i-mnt2), 1-ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate the chelating-bridging characteristics of the Et2dtc ligand and
(ecda2), diethyldithiocarbamate (Et2dtc), benzothiazole-2-thiolate the hetero-donor atoms ligands (bzta and XCN) yield
(bzta), 4,5-dimercapto-1,3-dithiole-2-thione (dmit2), bis(ethylenedithio)- mixed ligand heterobimetallic 1D polymers as is shown
tetrathiafulvalene (ET) and, 4,5-ethylenedithio-1,3-dithiole-2-thione (C5H4S5). in Fig. 22.
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Table 11 Summary of conductivity reported on pressed pellets with

the two probe method on 1D-CPs with sulfur ligands as linkers
Compound Conductivity/S cm1 Ref.

11 a
[Ag[Cu(ecda)2]2]n 10 107
[Pd[Cu(ecda)2]2]n 107 a 107
{(NEt4)[CuNi(dmit)2]}n 105 b 106
{(NEt4)[AgNi(dmit)2]}n 2 106 b 106
{(NEt4)[AuNi(dmit)2]}n 102 b 106
[Cu2Ni(dmit)2]n 6 104 b 106
[Ag2Ni(dmit)2]n 5 104 b 106
[Au2Ni(dmit)2]n 1.6b 106
[CuAu(dmit)2]n 106 b 106
[AgAu(dmit)2]n 3 107 b 106
[Au2(dmit)2]n 2 104 b 106
[Ag2Cu(i-mnt)2]n 106 a 105
[CdCu(i-mnt)2]n 109 a 105

[HgCu(i-mnt)2]n 106 a 105
[PbCu(i-mnt)2]n 107 a 105
[Ag2Ni(mnt)2]n 105 a 105 Fig. 22 Suggested polymeric structures for the heterobimetallic
[PdNi(mnt)2]n 105 a 105 complexes obtained with benzothiazole-2-thiolate (bzta), diethylthio-
[HgNi(mnt)2]n 105 a 105 carbamate (Et2dtc) and chalcogenocyanates (XCN) (X = S and Se)
(ET)CuI2Br4 1.6 102 b,c 109 ligands.
(ET)2CuI6Br10 2.5 b,c 109
(ET)2[Cu4Br6ET] 2.5 102 b,c 109
(ET)3CuI6Br10(H2O)2 5.1 102 b,c 109 electrical conductivity by 1 or 2 orders of magnitude. The
[Cu2C4S6] 0.1 b,d 110 smaller conductivity values found in the undoped polymers are
[NiC4S6] 0.9 b,d 110 explained by the authors as a result of weaker S S, S Se
[Ag(TTM-TTP)(CF3SO3)] 7 106 b 104

[Ag(C5H4S5)2NO3]In 3 105 b 104
and M S intermolecular interactions in the solid state.113
[Cu9(C5H5NS)8(SH)8]nn+ 1.6 103 b,c,d 111 Following the idea of preparing new materials combining
[Cu5(m-4-SpyH)7(m-I)I4]n 6.84 108 b,c 112 different physical properties such as conductivity and magnetism,
{[Cu2(m-I)(m-4-SpyH)3]I}n 2.74 109 b,c 112 R. Kanehama et al. have studied the reactions of Cu(II) halides
mnt2 = maleonitriledithiolate, i-mnt2 = isomaleonitriledithiolate, with bis(ethylenedithio)tetrathiafulvalene (ET)109 (Fig. 19).
dmit2 = 4,5-dimercapto-1,3-dithiole-2-thione, ecda2 = 1-ethoxycarbonyl- They obtained new charge transfer coordination polymers of
1-cyanoethylene-2,2-dithiolate, ET = bis(ethylenedithio)tetrathiafulvalene, formula (ET)CuI2Br4,(ET)2CuI6Br10, (ET)2[CuI4Br6ET] and
C4S62 = dithiolato, TTM-TTP = 2,5-bis-4 0 ,5 0 -bis(methylthio)-1 0 ,3 0 -
(ET)3CuI6Br10(H2O)2, where the ET ligands coordinated to
dithiol-2 0 -ylidene-1,3,4,6-tetrathiapentacene, C5H4S5 = 4,5-ethylene-
dithio-1,3-dithiole-2-thione, (C5H5N)S2 = 2,2 0 -dipyridyldisulfide, Cu(I) by the sulfur atoms of the ethylenedithio groups showing
4-SpyH = zwitterionic pyridium-4-thiolate. a 303–393 K. b 300 K different coordination modes. Unfortunately, the reduction of
and 1 bar. c Single crystal. d Four probe. the Cu(II) ions to Cu(I) precludes the coexistence of magnetic
and electrical properties in these compounds. The authors
classified the compounds into three different groups according
to the coordination modes of ET molecules. Group I: the ET
coordinates as a monodentate ligand (the authors obtained
discrete complexes with this mode of coordination). Group II:
the ET coordinates as trans-bidentate ligand. Group III: the ET
coordinates as cis-bidentate ligand. In the case of (ET)CuI2Br4,
a one-dimensional structure [ET–BrCu–(m2(Br)2–Cu(Br)–]n is
obtained, where the ET ligands are coordinated to two copper
ions with the two sulfur atoms in trans mode (Fig. 23). In
Fig. 21 Suggested polymeric structures consisting in [MNi(dmit)2] (ET)2CuI6Br10 complex, all the ET molecules coordinate to
units (M = CuI, AgI and AuI) interconnected by metallic centres. two copper ions with the two sulfur atoms in a cis-mode,
giving a one dimensional chain running along the c-axis
The proposed structures are based on various physico- (Fig. 24). Both structures present short interchain contacts
chemical studies and resemble those previously suggested for established by S S interactions.
similar ligands but, as in the previous cases, there is unfortunately
no X-ray structure of these polymers. Basically, the polymeric
structures of these heterobimetallic mixed ligands have the
Cu(II) and Ni(II) in square planar geometry, Ag(I) in linear
geometry and Hg(II), Cu(I) and Pb(II) are preferentially tetra-
hedrally coordinated.113
The electrical conductivity of these coordination polymers,
measured between 300–393 K in pressed pellets using the two
probe technique, shows low values of ca. 108–109 S cm1. Fig. 23 View of the one-dimensional chain [ET–(Br)Cu–(m2-Br)2–
Doping the polymers with iodine produces an increase in their Cu(Br)]N of (ET)CuI2Br4.
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of dithiolato C4S62 ligand with [Ni(H2O)6]Cl2 or

[Cu(MeCN)4]BF4. The analysis of the insoluble black solids
prompted the authors to propose the empirical formula
[Cu2C4S6] and [NiC4S6] with a 1D-polymeric structure. These
polymers are diamagnetic and show semiconducting properties
that have been attributed to the presence of a delocalized
p-electron system. Both [Cu2C4S6] and [NiC4S6] behave as
semiconductors with conductivity values of 0.1 and 0.9 S cm1
(measured at 294 K, using the four contact method). Despite
that the measurements were done in pressed pellets, these are
some of the better values so far reported. However, to clarify
this unusual conductivity their structures should be elucidated.
Following with the series of TTF derivatives, one dimensional
homometallic silver(I) coordination polymers obtained with

2,5-bis-4 0 ,5 0 -bis(methylthio)-1 0 ,3 0 -dithiol-2 0 -ylidene-1,3,4,6-tetra-
Fig. 24 Packing diagram of (ET)2CuI6Br10 projected along the c-axis. thiapentacene (TTM-TTP) and 4,5-ethylenedithio-1,3-dithiole-
2-thione (C5H4S5) (Fig. 19) ligands have also been studied.104,114
In the first case, the one dimensional coordination polymer
[Ag(TTM-TTP)(CF3SO3)] (Fig. 27) is obtained by slow diffu-
sion of n-hexane into a solution containing a mixture of
AgCF3SO3 and TTM-TTP in acetonitrile/benzene. In this
polymer, besides the Ag(I)–S coordination bonds, there are
extensive intermolecular S S contacts, providing additional
interactions across the individual chains.114

In the second case, the strong electron-donor C5H4S5 ligand
forms a one-dimensional silver(I) coordination polymer
with two parallel coordinating molecular units (Fig. 28). The
ligands coordinate to silver(I) through both sulfur atoms of the
Fig. 25 View of the ladder like structure of (ET)2[Cu4Br6ET].
thiocarbonyl and through the sulfur atoms of the thioether.
An additional extension of the contacts produces a 2D net-
The crystal structure of the (ET)2[Cu4Br6ET] polymer
work by strong S S interactions. The iodine doped complex
consists of two different parts. On one side the conducting
gives a room temperature conductivity of 3 105 S cm1
ET layers and, on the other, the ET-copper one-dimensional
measured in pressed pellets by a conventional two-probe
chains. In the ET layers, the ET molecules stack parallel to the
c-axis and are not coordinated to the copper ions. In the
ET-copper chains, the ET molecules coordinate to two copper
ions with the two sulfurs in a trans mode. Two quasi 1D
copper complexes [–Br–Cu–(m2-Br)2–Cu(Br)–]n bridged by
ET molecules form a ladder like structure (Fig. 25). This
compound is a hybrid material in which conducting layers
and a one-dimensional lattice coexist in the crystal packing.
In the complex (ET)3CuI6Br10(H2O)2, the ET molecules
coordinate to two Cu ions with the two S atoms in cis mode
(Fig. 26). Fig. 27 Side view of [Ag(TTM-TTP)(CF3SO3)] with face-to-face
The conductivity data obtained for these ET coordination S S contacts.
polymers, with the two-probe method on single crystals along
the c axis, using 15 mm gold wires and carbon paste, show that
these complexes are highly conducting materials (Table 11).
A very interesting work on 1D coordination polymers
with dithio ligands has been reported by Szczepura et al.110
They prepared several 1D-coordination polymers by reaction
Fig. 26 View of the zigzag one-dimensional chain of (ET)3CuI6Br10-

(H2O)2, projected along the a-axis. Fig. 28 Perspective view of [Ag(C5H4S5)2+]n.
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method and a semiconductor behaviour.104 As in other

already mentioned examples, the conductivity values of these
two polymers also increase when doped with iodine.
Recently, the use of new synthetic routes as solvothermal
(see Section 3.2 nucleobases as nitrogen ligands) and micro-
wave methods has led to the synthesis of interesting coordination
polymers with different architectures and dimensionalities.
One of these examples was obtained by microwave solvo-
thermal reaction of 2,2 0 -dipyridyldisulfide and Cu(BF4)2. The
reaction proceeds with an unusual cleavage of C–S and S–S
bonds of the 2,2 0 -dipyridyldisulfide ligand leading to a Cu(I)
1D-coordination polymer formation. The structure is generated
based on the assembling of Cu9 cages (Fig. 29).111 Fig. 30 Views of {[Cu2(m-I)(m-4-SpyH)3]n}n+ (up) and [Cu5(m-4-SpyH)7-
The unusual polymeric structure presenting a large number (m-I)I4]n (down).

of S bridges prompted the authors to measure its electrical
conductivity. Studies carried out at variable temperature reaction time. Thus, three different Cu/I/S-based coordi-
(Fig. 29), using the four probe technique, show a classical nation polymers were isolated: [Cu6(m-4-SpyH)4I6]n, {[Cu2(m-I)-
semiconductor behaviour with a high room temperature (m-4-SpyH)3]I}n, and [Cu5(m-4-SpyH)7(m-I)I4]n.112
conductivity of 1.6 103 S cm1.111 The process involves the in situ formation of the zwitterionic
Another polymer obtained under solvothermal conditions pyridinium-4-thiolate (4-SpyH) generated by S–S cleavage of
was synthesised by reaction of 4,4 0 -dipyridyl disulfide (dpds), the dpds ligand. The hexameric compound [Cu6(m-4-SpyH)4I6]n
oxalic acid and CuI.112 The products obtained depend on the forms a three dimensional diamond-like net, that will be discussed
in Section 5.2. The structure of the dimeric compound {[Cu2(m-I)-
(m-4-SpyH)3]I}n consists of a cationic {[Cu2(m-I)(m-4-SpyH)3]n}n+

polymeric chain with disordered iodides embedded between the
chains. In contrast, the pentameric compound [Cu5(m-4-SpyH)7-
(m-I)I4]n contains [Cu5(m-I)I4(m-4-SpyH)7] units that are inter-
connected with its neighbouring ones through two m-4-SpyH
bridges to form a neutral chain (Fig. 30). The formation of
these three different compounds provided an interesting example
that different coordination polymers could be produced from the
same components under solvothermal conditions at different
time periods, indicating that the often-neglected kinetic factors
may be very important in this kind of synthesis.
The thermal variation (from 293 to 443 K) of the electrical
conductivity measured for several single crystals of the dimeric
and pentameric compounds with the two probe technique
shows an exponential increase with increasing temperature
from 6.84 108 to 3.96 106 S cm1, for the dimeric
{[Cu2(m-I)(m-4-SpyH)3]I}n compound and from 2.74 109 to
2.43 107 S cm1, for the pentameric one, both displaying a
typical semiconducting behaviour. The authors attributed the
better conductivity of {[Cu2(m-I)(m-4-SpyH)3]I}n to the fact
that the density of states or effective mass in this compound is
larger than in the other one. In addition, the disordered
counter iodides and the weak Cu Cu interactions found in
compound {[Cu2(m-I)(m-4-SpyH)3]I}n may also contribute to
the increase in conductivity.112
3.5. Systems containing metallomacrocycles

The metallomacrocycles such as metallophthalocyanines and
metalloporphyrines have long been studied due to their interesting
applications like dyes, pigments, catalysts, electrical conductors,
etc. (Fig. 31).115
Fig. 29 Details of the structure of [Cu9(C5H5NS)8(SH)8]nn+ and Their typical structures provide poor p–p overlap between
thermal variation of the electrical conductivity with the scheme the adjacent molecules showing low electrical conductivities
of the 2,2 0 -dipyridyldisulfide ligand. (Data collected from ref. 111; usually in the range 1011–1013 S cm1.116,117 Collecting
reproduced by permission of the American Chemical Society.) these works, excellent reviews and articles about the
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Table 12 Summary of conductivity data reported on pressed pellets

with the four probe method in 1D-CPs containing metallomacrocycles

5 a
FePc(pyz)]n 2 10 126
[FePc(tz)]n 2 102 a 126
[RuPc(tz)]n 102 a 125
[FePc(me2-tz)]n 4 103 a 125
FePcOc 6.20 108 b,c 127
[FePcOC(dib)]n 5.73 107 b,c 127
Pc = phthalocyanines, pyz = pyrazine, tz = tetrazine, me2tz = 3,6-
dimethyl-s-tetrazine, MPcOc = octacyanometallophthalocyanines.
a
RT and 1 bar. b RT and 108 pa. c Two probe.
bridging ligands, for these compounds it seems that the use

of tetrazine allows significant increases of the semiconducting
Fig. 31 Schematic representation of 1D coordination polymers
properties without the need of external oxidative doping
composed of MPcs (Pc = phthalocyanine) molecules bridged with
(0.05–0.3 S cm1).127 Table 12 shows a selection of these
m-axial ligands.
polymers with the most significant conductivity values.
The improvement of the electrical properties by polymerizing
metallomacrocycle units into one-dimensional coordination
polymers seems to be a consequence of the partial electron
loss in the d(p)-orbital of the metal centre towards the bridging
ligand p/p* orbitals of the macrocycle ring.128 However,

most of these complexes are insoluble, and their purification
towards thin-film fabrication are therefore restricted. Attempts
to improve the solubility of these polymers by additional
functionalization of the macrocycle rings have been carried
Fig. 32 Example of an octacyanometallophthalocyanines polymer out. The case of the octacyanometallophthalocyanines
[FePcOc(dib)]n (Pc = phthalocyanine, dib = 1,4 diisocyanobenzene). (MPcOc) (Fig. 32) is an interesting example. In this case
strong electron acceptor properties have shown that this
electrical properties of these molecular materials have been material could be useful as very rare and stable n-type organic
published.118–120 semiconductors or as cathode material of lithium rechargeable
In order to improve the electrical conductivity, new types of batteries.127
low-dimensional compounds have been prepared where the Although functionalization leads to an increase in the
metallomacrocycles achieve a stacked co-facial arrangement solubility of the polymers, their electrical properties do not
with low interplanar distances allowing electron delocalization improve. Only a significant increase of the conductivity is
by p–p overlapping. This can be achieved using several observed by doping with lithium127 in both the monomeric
bridging ligands between the metallomacrocycles to generate (FePcOc) and polymeric [FePcOc(dib)]n (dib = 1,4-diisocyano-
a linear coordination polymer, where the central metal–axial benzene) complexes (Table 12).
ligand spine was expected to be a reasonable pathway for Therefore, despite the past and current interest in metallo-
conduction. phthalocyanines and metalloporphyrines as conductive
Among the large variety of semiconducting polymers based molecular materials,129 so far the electrical properties found
on metallophthalocyanines, the most important families are in coordination polymers containing these molecules as building-
the polyphthalocyaninato-metalloxanes [PcMO]n (M = Si, blocks have shown only moderate electrical conductivity values.
Ge, Sn), studied in detail by Kenney and Marks,121–123 and
those so-called ‘‘shish-kebab’’ developed by Hanack and Dini,
3.6. Aromatic hydrocarbons as linkers
based on the self-assembled Pc coordination polymers
(Fig. 32).124 Munakata et al. have been exploring the chemistry of poly-
A significant amount of these kind of coordination polymers cyclic aromatic hydrocarbons with different silver(I) metal
based on metallophthalocyanines and metalloporphyrines salts for decades (Table 13). They have described a vast body
with several bridging ligands, [MPc/P(L)]n (Pcs = phthalo- of literature comprising a good number of structurally charac-
cyanines, P = porphyrines; M = Fe, Co, Mn, Ru, Os; terised frameworks. The first record considering electrical
and L = cyano, pyrazine, tetrazine and many others bidentate conduction properties came in 1997130 when they isolated two
ligands), have been investigated as potential electrical unusual silver(I)-aromatic networks containing pyrene (pyr)
conductors.125,126 These compounds showed low conductivity and perylene (per) tectons, [Ag2(pyr)(ClO4)2] and [Ag2(per)(ClO4)2]
values in the lower part of the semiconducting region. However, respectively (Fig. 33), both displaying a tetra-Z2 coordination
doping these polymers with iodine increases conductivity up to mode, linking four metal centres and rendering W-shaped
values between 105–102 S cm1. In contrast to other polymeric chains and sheets, in this order.
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Table 13 Summary of conductivity data reported on single crystal at

room temperature and 1 bar with the two probe method on 1D-CPs
with aromatic hydrocarbons as linkers

6
[Ag4(rub)(ClO4)4(H2O)4], 1.9 10 131
[Ag4(bpyr)2(ClO4)4(toluene)2] 1.1 105 131
[Ag4(cor)3(ClO4)4], 3.1 103 131
[Ag3(bphen)(ClO4)3(H2O)2] 1.65 103–6.9 102 132
[Ag2(dban)(ClO4)2] 1.65 103–6.9 102 132
[Ag2(ban)(ClO4)2(H2O)] 1.65 103–6.9 102 132
[Ag2(napyr)(CF3SO3)2] 1.65 103–6.9 102 132
[Ag0.5(btp)0.5(ClO4)0.5] 1.32a 133
[Ag2(dbchry)(CF3SO3)2]- 5.77 102 134
[Ag2(toluene)2(CF3SO3)]n
[Ag4(bpyr)4(p-xylene)(ClO4)4]. 6.3 102 134
[Ag(dpbd)(ClO4)] 2.1 107 134

[Ag2(bmsb)(ClO4)2] 1.0 106 135
[Ag2(bmsb)(H2O)4](BF4)2 1.2 102 135
a
btp = 1,2-benztriphenylene. rub = rubrene, bpyr = benzo[a]pyrene, Fig. 34 View of the crystal structure of [Ag4(rub)(ClO4)4(H2O)4].
cor = corenene, bphen = benzo[a]phenanthrene, dban = dibenz[a,h]-
anthracene, ban = benz[a]anthracene, napyr = naphtho(2,3-a)pyrene,
btp = 1,2-benztriphenylene, dbchry = dibenzo[b,def]chrysene, bpry =
benzo[e]pyrene, dpbd = trans,trans-1,4-diphenyl-1,3-butadiene, bmsb =
1,4-bis(methylstyryl)benzene.
Fig. 35 Crystal structure of [Ag4(bpyr)2(ClO4)4(toluene)2].
A single crystal X-ray diffraction study of [Ag4(bpyr)2(ClO4)4-

(toluene)2] revealed a double helical arrangement sandwiching
Fig. 33 Solid-state molecular structure of [Ag2(pyr)(ClO4)2] (left) and a toluene solvent molecule, Z1- and Z2-coordination modes
[Ag2(per)(ClO4)2] (right) with partial numbering scheme. No hydrogen
for silver cations and an intricate interweaved network of
atoms are displayed.
aromatic p–p interactions (Fig. 35).
The solid-state structure of [Ag4(cor)3(ClO4)4] can be
A compressed powder pellet with the standard two-probe regarded as a triple-decker polymeric framework with both intra
method showed insulator behaviour for both species. However, and intermolecular p–p interactions warranting the formation of
I2-doping resulted on semiconduction with s values at room columnar stacks with very close contacts of 3.23 Å between
temperature of 1.7 105 and 4.4 105 S cm1 for adjacent corenene planes (Fig. 36).
[Ag2(pyr)(ClO4)2] and [Ag2(per)(ClO4)2], respectively. These No doping was needed to observe conductivity and the
values were postulated to be connected with the presence of recorded values measured at room temperature on a conven-
crystallised organic radicals, as evidenced by ESR spectroscopy. tional two-probe method on pressed pellets were 1.9 106,
In a later report, in 1998, the same authors succeeded in the 1.0 105 and 3.1 103 S cm1, for [Ag4(rub)(ClO4)4(H2O)4],
construction of new polymeric forms of organosilver compounds [Ag4(bpyr)2(ClO4)4(toluene)2] and [Ag4(cor)3(ClO4)4], respectively.
with strained aromatic moieties.131 This time rubrene (rub), In 1999, Munakata et al. extended this family of conducting
benzo[a]pyrene (bpyr) and corenene (cor) were combined with organosilver polymeric compounds with benzo[a]phenanthrene
Ag(ClO)4H2O to form novel polymeric networks formulated (bphen), dibenz[a,h]anthracene (dban), benz[a]anthracene (ban)
as: [Ag4(rub)(ClO4)4(H2O)4], [Ag4(bpyr)2(ClO4)4(toluene)2] and naphtho(2,3-a)pyrene (napyr) ligands.132 The reaction of
and [Ag4(cor)3(ClO4)4]. The most significant features of the these molecules with silver(I) salts generated herringbone-like
crystal structure of [Ag4(rub)(ClO4)4(H2O)4] are a 3D network architectures reminiscent of those of the free ligands. Thus, the
consisting of twisted rubrene fragments coordinated by eight crystalline solid state of [Ag3(bphen)(ClO4)3(H2O)2] consists of
silver cations with both Z1- and Z2-bonding modes, loose aromatic-linked chain strands along the c axis where each
of planarity of the rubrene fragment and lack of extended ligand adopts di-Z2 and tetra-Z2 coordination modes bridging
p–p interactions (Fig. 34). two and four metal centres, respectively. The existence of
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Fig. 36 The triple-decker motif observed on the molecular structure

of [Ag4(cor)3(ClO4)4] evidencing close p–p interactions.
Fig. 39 Solid state structure of [Ag2(ban)(ClO4)2(H2O)] with selected

atom labelling (up) and view of the multilayer framework depicted on
the ab plane (down).
silver ions are bonded to the head and tail of the aromatic
rings and to H2O molecules. The perchlorate counterions
exhibit mono and tridentate coordination modes and participate
in silver coordination through Ag–O–Cl–O–Ag and Ag–O–Ag
bonds (Fig. 39).
Although explicit details of electrical conduction for each
polymer were not given, authors claimed that on a two-probe
experiment with silver coated contacts the values observed for
Fig. 37 Atom labelling scheme (left) and herringbone disposition pressed pellets were in the range 1.65 103–6.9 102 S cm1
(right) of [Ag3(bphen)(ClO4)3(H2O)2]. at room temperature.
A striking feature in the structure of [Ag2(napyr)(CF3SO3)2]
intermolecular p–p interactions renders a supramolecular 2D is the presence of an unprecedented CF3SO3 group tricoordi-
sheet framework (Fig. 37). nated to a silver(I) ion. The herringbone pattern of the free
[Ag2(dban)(ClO4)2] exists in the solid state as a polymeric ligand is mainly retained giving rise to a 2D multilayer frame-
W-like sandwich of alternating AgClO4 and dban building- work with aromatic sheets suspended between pairs of infinite
blocks repeating along the b axis, each aromatic ring displays a ionic chains by Ag–O–S–O–Ag bonds (Fig. 40).
tetra-Z2 coordination bridging four metal ions. Extended In a later communication, Munakata et al. reported a new
intermolecular p–p interactions give rise to 2D sheets in the metallocyclophane with a columnar aromatic stacking.133 This
ab plane (Fig. 38). time the cyclophane motif was tethered through silver(I) ions
Similar multilayer 2D sheets are observed in the crystal rather than the previously reported C, O, S or N atoms, hence
structure of [Ag2(ban)(ClO4)2(H2O)] where two independent the unprecedented metallocyclophane nomenclature. When
the T-shaped 1,2-benztriphenylene (btp) ligand reacts with
AgClO4 in p-xylene, crystals with a [Ag0.5(btp)0.5(ClO4)0.5]
formulation could be isolated and their X-ray structure
determined (Fig. 41).
The btp ligand shows a di-Z2 coordination and is p–p face-
to-face stacked to parent aromatic units by two bridging Ag
centres. This repeating unit is further connected via ClO4
counterions affording a chain running along the b axis.
Additional intermolecular p–p interactions provide columnar
aromatic stacking of the argentocyclophane motifs. Note-
worthy, the electrical conductivity of a compressed pellet of
[Ag0.5(btp)0.5(ClO4)0.5] with a standard silver coated two-probe
Fig. 38 Crystal structure of [Ag2(dban)(ClO4)2] (left). View of the 2D method revealed the highest value of all characterised organo-
multilayer structure along the ab plane (right). silver complexes with s = 1.32 S cm1 at room temperature.
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Fig. 42 Crystal structure of [Ag2(dbchry)(CF3SO3)2][Ag2(toluene)2-

(CF3SO3)]n co-crystallised species.
Fig. 40 Crystal structure of [Ag2(napyr)(CF3SO3)2] showing coordi-

nation environments for silver centres and atomic labelling scheme
(top). Depiction of herringbone pattern retention (bottom).
Fig. 43 Solid state structure of the tetranuclear species [Ag4(bpyr)4-

(p-xylene)(ClO4)4] (left) and arrangement of the stacking polymer (right).
two pairs of ClO4 counterions interacting via intermolecular

p–p contacts through extra pendant bpyr ligands, leading to a
2D sheet structure together with a 1D columnar stacking
(Fig. 43).
The room temperature electrical conductivity values, measured
with the two probe method, are 6.3 102 S cm1 in
[Ag4(bpyr)4(p-xylene)(ClO4)4] and 5.8 102 S cm1 in
[Ag2(dbchry)(CF3SO3)2][Ag2(toluene)2(CF3SO3)]n.
Extending their postulate to multiphenyl dienes, Munakata
Fig. 41 Argentocyclophane structure of [Ag0.5(btp)0.5(ClO4)0.5] (top)
et al. reported another semiconducting polymer in 2003.134
and evidence of intra and intermolecular p–p interactions (down). trans,trans-1,4-Diphenyl-1,3-butadiene (dpbd) was reacted
with AgClO4 to yield [Ag(dpbd)(ClO4)] as colourless crystals.
Its structure shows a trigonal local environment for the silver
In 2001 the same authors reported three new complexes of atom formed by Z1-bonds to two phenyl fragments and an
silver(I) with benzopyrene and two of them were found to oxygen atom from a ClO4 group. The dpbd coordinates two
be semiconductors.134 Single yellow crystals of [Ag2(dbchry)- metal atoms building a 1D W-shaped infinite chain that stacks
(CF3SO3)2][Ag2(toluene)2(CF3SO3)]n were obtained combining forming a herringbone (Fig. 44). Its electrical conductivity
Ag(CF3SO3) and dibenzo[b,def]chrysene (dbchry). Its crystal shows a room temperature s value of 2.1 107 S cm1.
structure can be described as a 2D layer presenting cation–p The last work published by Munaksta’s group concerning
interactions of Ag(I) and dbchry together with a 1D polymer silver metal–organic frameworks relates to another multiphenyl
formed by Ag(I) and solvent toluene molecules (Fig. 42). diene ligand.135 The new complexes [Ag2(bmsb)(ClO4)2] and
On the border limits of the scope of this review stands [Ag2(bmsb)(H2O)4](BF4)2 (bmsb = 1,4-bis(methylstyryl)benzene)
the stacking polymer formed by the reaction of Ag(ClO4) with displayed s values of 1.0 106 and 1.2 102 S cm1,
benzo[e]pyrene (bpyr): [Ag4(bpyr)4(p-xylene)(ClO4)4]. This respectively (Fig. 45 and 46). Attending to their crystal
polymer presents a tetranuclear core formed by two crystallo- structure, the presence of columnar stacking in the latter but
graphically different Ag(I) centres, two symmetry related not in the former might be responsible for the enhanced
bpyr molecules sandwiching a p-xylene solvent molecule and electrical conductivity observed.
View Online
4. Two dimensional coordination polymers

4.1. 2D polymers with inorganic linkers
Mixed-valence dinuclear species have proved to be resourceful
building-blocks for the preparation of coordination polymers
with notable electrical properties. Thus, Kawamura and
colleagues have been exploiting the [Rh2(acam)4(H2O)2]
(acam = acetamidato) dimer in order to generate networks
Fig. 44 Waved infinite chains of [Ag(dpbd)(ClO4)]. with different dimensionalities. In 2003 they constructed a 2D
honeycomb-like frame employing [Rh2(acam)4] as its neutral
and radical cation (Rh24+ and Rh25+) forms linked by m3-Cl
halides.136 The reaction between [Rh2(acam)4(H2O)2]6H2O
or [Rh2(acam)4(H2O)2]ClO4 with excess NaCl gave
[{Rh2(acam)4}3(m3-Cl)2]n4nH2O. Higher concentration of

the radical salt resulted in the formation of the previously
reported [Rh2(acam)4Cl]n crystals (Fig. 11). The structure of
[{Rh2(acam)4}3(m3-Cl)2]n4nH2O consists of honeycomb layers
in the bc plane (Fig. 47). The layers are formed by hexagons
containing six [Rh2(acam)4] dimers in the sides and six Cl
ions in the corners. Attending to the Rh–O and Rh–N bond
distances, there exists both Rh24+ and Rh25+ units in a 1 : 2
ratio, giving rise to an average Rh2(14/3)+ oxidation state.
Solvent water molecules are sandwiched between layers forming

an intricate hydrogen-bond network. The authors postulated
that these hydrogen bonds favour a localization in the metal’s
Fig. 45 Supramolecular 2D structure observed on [Ag2(bmsb)(H2O)4]- oxidation state responsible for the low electrical conductivity
(BF4)2 where both intra and interchain p–p contacts extend in columnar of the network, with a value of 2 107 S cm1 measured on a
stacking (top). Portion of the molecular structure (bottom). pressed pellet at room temperature.
Following their studies with the Rh2(acam)4 building block,
In the solid state structure of [Ag2(bmsb)(H2O)4](BF4)2 Fuma and Ebihara prepared in 2006 a 2D square-sheet
(Fig. 45) the ligand face-to-face arrangement is secured via comprising this unit linked with ReO4 ions.137 This was the first
double silver m-tetra-Z2 bridges forming a metallocyclophane example of a perrhenate ion bonded to four metal complexes.
moiety with a chain structure. Strong contacts, both intra and The structure of [{Rh2(acam)4}2(m4-ReO4)] consists of equivalent
interchain, generate a supramolecular 2D network. Rh2 units linked by ReO4 ions as stacked square sheets in the
On the other hand, a cyclophane motif is also observed for bc plane. There are amido-NH and amido-O inter-layer
[Ag2(bmsb)(ClO4)2] (Fig. 46). These cyclic structures give rise hydrogen bonds (Fig. 48). The intra-dimer Rh–Rh distance
in the solid state to a supramolecular 2D polymer constructed is 2.4047(6) Å. The network was assembled mixing equimolar
by 1D chains where equivalent silver(I) centres bond to both
phenyl and vinylene fragments of bmsb. The metal coordina-
tion sphere is completed with oxygen atoms of different ClO4
groups. Moreover, no p–p intrachain interactions are observed
whereas close interchain contacts of 3.42 Å between phenyl
and CQC are present.
Fig. 46 Pseudo-cyclophane moiety observed in the molecular struc-

ture of [Ag2(bmsb)(ClO4)2] (left) and single sheet component along the Fig. 47 Honeycomb structure of [{Rh2(acam)4}3(m3-Cl)2]n4nH2O,
ab plane (right). some of the hydrogen atoms have been omitted for clarity.
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Fig. 48 Top (left) and side (right) view of the square sheet formed by
[{Rh2(acam)4}2(m4-ReO4)]. Only hydrogen atoms involved in hydrogen
bonding are displayed.
Table 14 Conductivity reported at room temperature and 1 bar on

pressed pellets with the two probe method on 2D-CPs with inorganic
linkers

[{Rh2(acam)4}3(m3-Cl)2]n4nH2O 2 107 136
[{Rh2(acam)4}2(m4-ReO4)] 8.9 106 137
acam = CH3CONH2.
amounts of [Rh2(acam)4(H2O)2]6H2O and [Rh2(acam)4(H2O)2]-

ClO4 with excess NH4ReO4, a common procedure for these type
of arrays. The electrical conductivity of [{Rh2(acam)4}2(m4-ReO4)]
as a pressed pellet at room temperature was 8.9 106 S cm1
(Table 14).
4.2. 2D polymers with nitrogen-containing ligands

Fig. 49 View of the copper environments in [Cu2Br(IN)2]n (top left).
P. Amo-Ochoa et al. have synthesized a 2D multifunctional View of a single layer framework (top right). Superposition of layers
mixed-valence Cu(I/II) coordination polymer [Cu2Br(IN)2]n along the a axis (bottom).
(IN = isonicotinate = py–COO) presenting conducting,
magnetic and luminescent properties (Fig. 49).
Its structure consists of pairs of copper atoms bridged by
two isonicotinato ligands and a bromide ion. The fourth
coordination site of the copper ion is occupied by an additional
terminal N-coordinated isonicotinato ligand. The geometry of
this entity forms four-arm units which propagate along the
bc plane in a 2D-framework (Fig. 49). Stacking of layers along
the a axis results in a 3D organization with p-stacking between
isonicotinato aromatic rings (3.36 Å). The electrical charac-
terisation of the crystals, carried out by the two contacts method,
showed semiconductor behaviour with a conductivity value of
1.2 105 S cm1 at room temperature.
The singular crystal structure and its multifunctional Fig. 50 Structure of Ag2CA (CA = cyanuric acid) showing the Ag
features prompted the authors to exfoliate the crystals by sheets and CA chains.
means of ultrasounds. In such a way single-layers were isolated
on mica and characterized by atomic force microscopy and The presence of two-dimensional Ag sheets is expected to give
XPS. This result suggests that 2D-coordination polymers can be rise to anisotropic conductivity. Accordingly, the values of the
considered as alternative materials to graphene.138 room temperature dc conductivity, parallel and perpendicular to
Rao et al. have studied supramolecular assemblies of the Ag sheets (bc plane) are ca. 5 103 and ca. 2 105 S cm1,
cyanuric acid (CA) involving both hydrogen bonding and respectively. The conductivity along the sheets is temperature-
metal ion-coordination capabilities. Thus, during the course independent down to 15 K (Table 15).
of their investigations, Rao et al. isolated a novel silver
4.3. 2D polymers containing organosulfur ligands
compound: Ag2(CA) (Fig. 50), whose structure presents two
dimensional Ag sheets with the cyanuric acid molecules in the As it has already been described (Section 3.4) the sulfur rich
interlayer space, forming linear hydrogen bonding.139 4,5-ethylenedithio-1,3-dithiole-2-thione (C5H4S5) presents
View Online
Table 15 Conductivity data reported at room temperature and 1 bar Table 16 Conductivity data reported at room temperature and 1 bar
on single crystals with the two probe method on 2D-CPs containing on pressed pellets with the two probe method on 2D-CPs containing
nitrogen donor ligands organosulfur ligands
Compounds Conductivity/S cm1 Ref. Compounds Conductivity/S cm1 Ref.

5 12
[Cu2Br(IN)2]n 1.2 10 138 [Ag(C5H4S5)CF3SO3]n o10 104
Ag2(CA) 5 103 a 139 Ni2(C4N2H3S)4 5 103 140
2 105 b [{Ag(C5H4NS)}]n 2.04 105 141
a CuHT 120 142
Isonicotinato = IN, cyanuric acid = CA. Parallel to the bc plane.
b C5H4S5 = 4,5-ethylenedithio-1,3-dithiole-2-thione, C4N2H3S =
Perpendicular to the bc plane.
pyrimidine-2-thiol, C5H4NS = pyridine-2-thiolate (PyS), HT =
4-hydroxythiophenolate.
Fig. 51 Schematic representation of the two dimensional network of

[Ag(C5H4S5)CF3SO3]n.
different available sites that can coordinate to metal ions. Fig. 52 View of a layer of compound Ni2(C4N2H3S)4.
Furthermore, thanks to its capacity to act as an electron-donor,
it has been considered as a good candidate for the synthesis Ni2(C4N2H3S)4 (Fig. 52) presents electrical conductivity and
of donor–acceptor metallic systems. As mentioned before ferromagnetic interactions between the Ni(II) centres. The
(Section 3.4), Jie Dai et al. used this ligand to prepare 1D conductivity measurement (in pressed pellets) of 5 103 S cm1
coordination polymers and, interestingly, a modification of the at room temperature increases upon heating, indicating typical
reaction conditions between C5H4S5 and AgCF3SO3 lead to the semiconductor behaviour. The semiconducting properties may
synthesis of the 2D-coordination polymer [Ag(C5H4S5)CF3SO3]n.104 be attributed to the presence of an interconnected array of
In this polymer, there are two independent silver(I) atoms nickel(II) ions with pyrimidine presenting some Ni(II)-pyridine
(types A and B), both showing a five coordinate environment. ring interactions.
Type A silver atoms have a S4O donor set and are coordinated The second example with a pyrimidyl nitrogen-containing
by four thiocarbonyl sulfur atoms from four different C5H4S5 thiol is an interesting 2D-polymer synthesized by Su et al.141
molecules and one oxygen atom from a triflate anion (CF3SO3). using pyridine-2-thiolate as building-block. This polymer of
Type B silver atoms are surrounded by a S2O3 donor set from formula [{Ag(C5H4NS)}]n (C5H4NS = pyridine-2-thiolate
two thioether sulfur atoms and three oxygen atoms of triflate (PyS)) shows a graphite-like array of silver(I) ions (Fig. 53).
anions (Fig. 51). Its structure consists of sheets where the silver atoms are
[Ag(C5H4S5)CF3SO3]n presents short S S distances, indi- connected by PyS ligands to generate layers with the pyridyl
cative of an efficient intermolecular p–p orbital interaction, groups of the PyS ligands inserted into the interlayer region
usually related with an increase in the electrical conductivity. (the interlayer distance is 17.17 Å). Each PyS ligand acts
Since the mixed-valence oxidation state (partial-oxidation, as a m3 bridge to link two silver atoms through a S atom, and a
reduction, or charge-transfer) is a key feature in many conducting third silver atom through a N atom. Each silver atom is
compounds, this polymer was partially oxidized by iodine- coordinated by two S atoms and one N atom. The electrical
doping. The studies of the electrical properties of this material conductivity measured in a pressed pellet is 2.04 105 S cm1
showed that although the coordination polymer is an insulator at 298 K, with a semiconducting behaviour that was attributed
with s o 1012 S cm1 (measured in pressed pellets at 300 K to the presence of Ag–Ag interactions.141
and using the two probe method, Table 16), the iodine-doped
product behaves as a semiconductor with a room temperature
conductivity of 1.5 104 S cm1.104
In an attempt to solve the insolubility problems found in
metal thiolate compounds, some authors have used pyrimidyl
nitrogen-containing thiols as ligands to generate crystalline
networks with metal ions such as Ag(I) or Ni(II). Two examples
are reported in the literature with these kind of ligands.140
The first one describes a 2D-coordination polymer obtained
by a solvothermal reaction between pyrimidine-2-thiol and Fig. 53 A view of the lamella structure of [{Ag(C5H4NS)}]n (left).
Ni(OAc)2 in DMF/H2O.143 The lamellar structure of formula Graphite-like structure formed by Ag metal centres (right).
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Fig. 54 Crystal structure of isostructural [{Ag(C5H5NS)2}(BF4)2]n

and [{Ag(C5H5NS)2}(ClO4)2]n chains (left). Ladder chain observed
in the molecular structure of [{Ag4(C5H5NS)6}(NO3)4]n (right). Non-
coordinating counterions and H atoms are not shown for clarity.
On a subsequent study, two years later Su et al. described

different coordination modes of the pyridine-2-thiolate
(and/or thione) (Spy and/or HPyS, respectively) upon silver(I)
complexation.144 Several polymers were described and X-ray
diffraction analyses of all compounds were collected.
Although precise data on their electrical conductivity were
not provided, the s values found were typical of insulators, Fig. 56 The 1D chains observed in the solid state structures of
with values in the range 1012 to 1015 S cm1 at 25 1C. [Ag4(m4-i-mnt)2(m-HPyS)2(m-HPyS)4/2]n (top) and [Ag4(m3-S2CNEt2)2-
Soaking [{Ag(C5H4NS)}]n in DMF for one month gave rise (m2-SPy)4/2]n (bottom).
to the isomer [{Ag6(C5H4NS)6}]n. In the absence of water and

using MeCN rather than DMF, [{Ag(C5H5NS)2}(BF4)2]n was 5. Three dimensional coordination polymers
obtained. In the same way [{Ag(C5H5NS)2}(ClO4)2]n was
synthesised from AgClO4 and [{Ag4(C5H5NS)6}(NO3)4]n from 5.1. 3D coordination polymers with inorganic linkers
AgNO3. The BF4 and ClO4 salts are best described as In a short communication in 2004, Kawamura et al. reported
isostructural cationic metal–metal-chains whereas the NO3 the isolation of a 3D diamond-like network built with
salt forms a 1D pseudo-ladder chain (Fig. 54). Rh2(acam)4 paddle-wheel complexes connected via m4-iodide
Another layered polymer was isolated from the reaction between bridges.145 The slow evaporation of an aqueous solution with
pyridine-2-thiol (HPyS) and AgBF4 in MeOH : CH3CN (40 : 1), [Rh2(acam)4(H2O)2]6H2O, [Rh2(acam)4(H2O)2]ClO4 and NaI
in this way [{Ag5(Spy)4(HPyS)}BF4]n was assembled (Fig. 55). produced the [{Rh2(acam)4}2I]n6nH2O network (Fig. 57).
The reaction of K2(i-mnt) with HPyS and AgNO3 furnished
the polymeric chain [Ag4(m4-i-mnt)2(m-HPyS)2(m-HPyS)4/2]n
(Fig. 56). Finally, when HPyS, NaS2CNEt2 and AgNO3
were combined another polymeric 1D species resulted,
[Ag4(m3-S2CNEt2)2(m2-SPy)4/2]n (Fig. 56).
Recently, Che et al. have reported an unprecedented 2-D
Cu–S coordination polymer formed by self-assembly of Cu(I)
ions with 4-hydroxythiophenol. Its X-ray structure solved by
using powder X-ray diffraction data agrees with the lamellar
architecture of CuHT (HT = 4-hydroxythiophenolate). The
self-assembled coordination network displays ionic behaviour
with a bulk electrical conductivity value measured on pellets at
room temperature of 120 S cm1.142
Fig. 57 Diamond network of [{Rh2(acam)4}2I]n6nH2O (top left),

only Rh and I centres are represented for clarity. Arrangement of
[{Rh2(acam)4}2I]n network (bottom left) showing the unusual m4-I
coordination mode. Solvent water molecules are located around the
iodine site (top right). Electrical conductivity oscillation observed for a
pressed pellet of [{Rh2(acam)4}2I]n during dehydration and rehydration
cycles (bottom right). (Data collected from ref. 145; reproduced by
Fig. 55 2D lamellar structure of [{Ag5(Spy)4(HPyS)}BF4]n. permission of the American Chemical Society.)
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Table 17 Conductivity data reported at room temperature and 1 bar

on pressed pellets with the two probe method on 3D-CPs with
inorganic linkers

3
[{Rh2(acam)4}2I]n6nH2O 1.4 10 145
7.0 109a
a
acam = CH3CONH2. Dehydrated sample.
X-Ray diffraction analyses revealed the presence of equivalent

Rh2 and m4-I units arranged on a diamond framework with
water solvent molecules occupying the interstitial holes. There
are inter-dimer hydrogen bonds formed between all amido-NH
and amido-O that extend to the co-crystallised water molecules.

Interestingly, the solvent molecules play a key role in the
electrical conductivity of the polymer, a pressed pellet of
[{Rh2(acam)4}2I]n6nH2O displayed a room temperature electrical
conductivity of 1.4 103 S cm1 that decreases to
7.0 109 S cm1 when the sample dehydrates (Table 17).
Exposing compound to moisture resulted in both the recovery
of the [{Rh2(acam)4}2I]n6nH2O formulation, as inferred by Fig. 59 Several views of the structure of [Cu6(m-4-SpyH)4I6]n.
X-ray powder diffraction analyses, and an upturn in the
electrical conductivity which scopes over a range of 105 during
dehydration–rehydration cycling. The authors claimed that and [Cu5(m-4-SpyH)7(m-I)I4]n112 (the two last ones are
the diamond structure persisted over those cycles. one dimensional polymers that were already described in
Section 3.4). The first complex [Cu6(m-4-SpyH)4I6]n has an
5.2. 3D coordination polymers with organic linkers adamantine-type Cu6S4 core. The four equatorial Cu(I) atoms
are tetrahedrally coordinated by two bridging I atoms and
One of the most notable examples of conductivity in coordi- two S atoms from two 4-SpyH ligands while the two apical
nation polymers are the compounds Cu(R1,R2-DCNQI)2, Cu(I) centres are trigonally coordinated by one terminal iodide
where R1, R2 = H, Cl, Br, I, Me, OMe and DCNQI = and two sulfur atoms from one 4-SpyH ligand. Each [Cu6S4]
N,N 0 -dicyanoquinonediimine. Their structures contain seven core acts as a tetrahedral 4-connecting node and is linked with
interpenetrating diamond nets, with infinite stacks of DCNQI four other equivalent [Cu6S4] cores through four pairs of
radical anions (Fig. 58). The copper atoms have an average iodide bridges coordinated to the equatorial Cu(I) ions, forming
oxidation state of +1.33 and the series show metal-like a 3D diamond-like network (Fig. 59). All these features suggest
conductivities. The dimethyl derivative, for example, has a that this 3D network may not be robust enough to survive
conductivity of 103 S cm1 at room temperature.146 at solvothermal conditions and may dissociate into other
As we already mentioned in Section 3.4, the solvothermal more stable species if the time of this reaction is deliberately
synthetic methods may give rise to new interesting supramolecular prolonged. The conductivity of the crystal increased exponen-
structures. For example, reaction of CuI with 4,4 0 -dipyridyl tially from 1.97 109 S cm1 to 6.32 107 S cm1, upon
disulfide (dpds) and oxalic acid at three different time periods heating from 293 to 443 K.
allowed the isolation of three Cu/I/S-based coordination Cao et al. reported in 2002 a novel 3D polymer constructed
polymers, [Cu6(m-4-SpyH)4I6]n, {[Cu2(m-I)(m-4-SpyH)3]I}n, from silver(I) metal centres and benzene-1,3,5-tricarboxylic
acid (H3btc).147 Slow diffusion of methanolic AgNO3 over
aqueous H3btc gave rise to the formation of the polymeric
[{Ag(H2btc)2}{Ag2(Hbtc)}]n compound. Its crystal structure
shows the existence of two interpenetrated distinct building
blocks: Ag8(Hbtc)12/3 (A unit) and Ag2(H2btc)2 (B unit)
(Fig. 60). The intricate structure can be rationalised as distorted
ladder-like chains of Ag atoms (Fig. 61) bridged by both
H2btcand Hbtc2 spacers. Remarkably, the whole structure
is sustained by direct Ag–Ag interactions.
The electrical conductivity, measured on pressed pellet
showed a s value of 1.06 106 S cm1 at room temperature
that increased with increasing temperature in a semiconducting
regime.
In 2004, the group of Wu described a new 3D silver
Fig. 58 Solid-state structure of [Cu(2,5-dimethyl-DCBQI)2]n projected organodiphosphonate framework: [Ag4(O3PCH2CH2PO3)],148
over the ab plane. with a zeolite-like structure sustaining a sub-lattice with direct
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Table 18 Conductivity data reported at room temperature and 1 bar

on pressed pellets with the two probe method on 3D-CPs with organic
linkers

3
Cu((CH3)2DCNQI)2 10 147
[Cu6(m-4-SpyH)4I6]n 1.97 109 115
6.32 107 a
[{Ag(H2btc)2}{Ag2(Hbtc)}] 1.06 106 148
[Ag4(O3PCH2CH2PO3)], 7 107 b 149
DCNQI = N,N 0 -dicyanoquinonediimine, benzene-1,3,5-tricarboxylic
acid = H3btc. a 443 K. b 170 1C.
6. Conclusions and perspectives

Fig. 60 Structure of [{Ag(H2btc)2}{Ag2(Hbtc)}]n showing the A units

Ag8(Hbtc)12/3 (up) and the B units Ag2(H2btc)2 (down). In the past few decades, the synthesis and characterisation of
low-dimensional crystalline conducting materials has attracted
much interest due to their highly tuneable structures and their
potential applications in electronics and optoelectronic devices.149
Coordination polymers are currently one of the hottest
topics in Inorganic and Supramolecular Chemistry (see for
Fig. 61 Silver chain network formed by direct Ag–Ag interactions in instance the excellent review by C. Janiak that is now receiving
[{Ag(H2btc)2}{Ag2(Hbtc)}]n.
over 200 citations a year and the special volume devoted in this
journal to MOFs).150 There is no doubt of the technological
impact expected for coordination polymers within the next

coming years, in fact some of them are already being used in
industrial applications.
Despite the electrical conductivity not being the prime focus
of research, several conductive coordination polymers have
been reported in the last few decades. We have shown that this
tendency seems to be changing due to the current interest in
the development of highly conducting coordination polymers
aimed for novel technological applications: porous electrode
for batteries, fuel cells, capacitors, sensors, nanomaterials,
etc.6,7,151 Thus, from the pioneering works of Interrante
Fig. 62 The zeolite-like arrangement of [Ag4(O3PCH2CH2PO3)] et al. in the 70’s on the MX chains and of Bellitto et al. in
showing its channel structure (left). Substructural network constructed the 80’s on the MMX chains, the number of conducting CPs of
through Ag–Ag bonding interactions (right). these and other families has shown an exponential increase
with time. This huge rise is the logical consequence of the
increase in the number of used metals and ligands (either as
linkers or as chelating units). Thus, besides the initial examples
with Pt, Pd and Ni, here we have seen that many other metals
such as Ag, Rh, Ru, Cu, Au, Fe,. . . can also be used to prepare
CPs. The number of bridging ligands has also increased from
the initial simple halides to more complex ones such as CN,
NO3, SCN, SeCN, N3, pyrazines, nucleobases, diverse
S-containing ligands and aromatic hydrocarbons,. . . The
chelating ligands stabilising the structure and completing
the coordination environment of the metal atoms have also
increased from the initial alkyldiamines (en, tn, bn and chxn)
and carboxylates to more complex ones such as dithiomalon-
Fig. 63 Temperature dependence of the electrical conductivity found
amide, thioureas, thioamides, dibenzyl sulfide, diphosphites,
for [Ag4(O3PCH2CH2PO3)] (Reproduced from reference 148 with
dithiocarboxylates, acetamides, TTF-type donors, dithiolates,. . .
permission of Elsevier).
In this review we have tried to summarize the state-of-the-art
in this topic collecting the vast number of compounds struc-
Ag–Ag contacts (Fig. 62). The electrical conductivity of turally and electrically characterized that were disperse in the
a polycrystalline pellet showed maximum values at 170 1C literature (in some cases there were no clear relationship
of ca. 7 107 (Fig. 63). between the reported examples). This compilation has also
Table 18 collects the conductivity data reported on 3D-CPs shown a large dispersion of the experimental conductivity
with organic linkers. values (from highly conducting CPs with room temperature
View Online
conductivities above 102 S cm1 to very poor semiconductors References and notes
with room temperature conductivities below 1014 S cm1).
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pellets, thin films or even nanowires with just a few molecular M. Eddaoudi and J. Kim, Nature, 2003, 423, 705–714.
chains. The thermal variations cover a wide range of temperatures 5 D. Tanaka, K. Nakagawa, M. Higuchi, S. Horike, Y. Kubota,
L. C. Kobayashi, M. Takata and S. Kitagawa, Angew. Chem., Int.
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Chemical Society Reviews

Cite this: Chem. Soc. Rev., 2012, 41, 115–147

www.rsc.org/csr CRITICAL REVIEW

1. Introduction is somehow based on the properties found between both types

Gonzalo Givaja studied Pilar Amo-Ochoa received a

coordination polymers (PCPs). These PCPs or MOFs can be

discipline. However, in the near horizon new amazing applications

conductors and most of the low-dimensional conductors often

Carlos J. Gómez-Garcı´a was Fe´lix Zamora was born in

resistivity is the physical magnitude showing the largest range

(Scheme 1). passes from B to C), the resistance is measured by applying a

occupied and unoccupied orbitals will bear one electron

Fig. 1 Schematic representation of mixed-valence MX, charge density

MX-chains species have been reported so far by applying this

A special case of conductivity in CP is the neutral linear-

pressure played a role in reducing the geometrical inequivalency

(b) [Pt(en)2][Pt(en)2Br2](ClO4)4 and (c) [Pt(en)2][Pt(en)2I2](ClO4)4.

those of the corresponding Pt analogues (Table 1). For instance,

for this complex compared with all the other halogen-bridged

3.1.1.2. Ni MX chains. Conversely to Pt and Pd species, due

divalent discrete compounds in the presence of a pertinent

Table 3 Summary of conductivity data reported for 1D hetero-

Compounds Conductivity/S cm1 Ref.

Fig. 6 Scheme of the 1D polymers synthesised by Castan et al.65–67

are best formulated as [MII(HL)2][MIVX6] and [MII(HL)2]-

depicted in Fig. 6. Their proposed MII X–MIV–X structures

the M–M interaction. The resulting geometries have been

3.1.4. MMX chains. When two metal centres are bridged

intermediate regime between the metallic and semiconducting

While continuous reports concerning Pt2(RCS2)4I have

Fig. 10 A fragment of the molecular structure of K4[Pt2(pop)4I] species,

Compounds Conductivity/S cm1 Ref.

repeating units, forming zig-zag chains in the two ﬁrst cases

display several coordination modes when bridged by halides,

Fig. 15 Solid-state structure of {[PPh4]2Te2Ru4(CO)10Cu4Br2Cl2)

perpendicular chain direction, crystal thin plate morpho-

Fig. 17 One dimensional structure of [{Cu(TANC)}F0.5]n with alter-

more important, to design coordination polymers with the

3.4. Sulfur ligands as linkers

Table 11 Summary of conductivity reported on pressed pellets with

Compound Conductivity/S cm1 Ref.

[CdCu(i-mnt)2]n 109 a 105

[Ag(TTM-TTP)(CF3SO3)] 7 106 b 104

of dithiolato C4S62 ligand with [Ni(H2O)6]Cl2 or

homometallic silver(I) coordination polymers obtained with

interactions across the individual chains.114

Fig. 26 View of the zigzag one-dimensional chain of (ET)3CuI6Br10-

method and a semiconductor behaviour.104 As in other

The unusual polymeric structure presenting a large number (m-I)I4]n (down).

(m-4-SpyH)3]I}n consists of a cationic {[Cu2(m-I)(m-4-SpyH)3]n}n+

3.5. Systems containing metallomacrocycles

Table 12 Summary of conductivity data reported on pressed pellets

Compounds Conductivity/S cm1 Ref.

bridging ligands, for these compounds it seems that the use

ligand p/p* orbitals of the macrocycle ring.128 However,

Table 13 Summary of conductivity data reported on single crystal at

Compounds Conductivity/S cm1 Ref.