Derivatization of Bichromic Cyclometalated Ru (II) Complexes With Hydrophobic Substituents

Derivatization of Bichromic Cyclometalated Ru(II) Complexes with
Hydrophobic Substituents
Kiyoshi C. D. Robson, Bryan D. Koivisto, and Curtis P. Berlinguette*
Department of Chemistry, Institute for Sustainable Energy, Environment and Economy, and Centre for Advanced Solar Materials,
University of Calgary, 2500 University Drive Northwest, Calgary, Alberta, Canada T2N 1N4
*S Supporting Information
ABSTRACT: The syntheses and physical properties of cyclometalated Ru(II) complexes
containing a triphenylamine (TPA) unit bearing aliphatic groups are reported. Each member of
the series consists of an octahedral Ru(II) center coordinated by a tridentate polypyridyl ligand and
a tridentate cyclometalating ligand. One of the chelating ligands contains electron-deficient methyl
ester groups, while a TPA unit is attached to the central ring of the adjacent chelating ligand through
a thiophene bridge. This study builds on our previous work (Inorg. Chem. 2011, 50, 60196028;
Inorg. Chem. 2011, 50, 54945508) by (i) outlining a synthetic protocol for installing aliphatic
groups on the TPA substituents, (ii) examining the role that terminal O-hexyl and S-hexyl
groups situated on the TPA have on the electrochemical properties, and (iii) demonstrating the
potential benefit of installing the TPA on the neutral chelating ligand rather than the anionic
chelating ligand. The results reported herein provide important synthetic advances for our broader
goal of developing bis-tridentate cyclometalated Ru(II) complexes for light-harvesting applications.
INTRODUCTION
There has been a recent renaissance in the design and study of
cyclometalated Ru(II) complexes in light of their proven utility
in solar energy conversion schemes
17
and biological
applications.
810
This interest is rooted in the broad absorption
profiles and well-defined redox behavior stabilities for this class
of compounds.
1117
Moreover, the presence of a single anionic
cyclometalating ligand about an octahedral Ru center that is
coordinatively saturated by neutral polypyridal ligands induces
an electronic asymmetry that offers acute control of the frontier
molecular orbitals.
2,18
Consequently, the thermodynamic
positions of the highest occupied molecular orbital (HOMO)
and lowest unoccupied molecular orbital (LUMO) can be
easily modulated through judicious installation of substituents
on the anionic and neutral ligands, respectively.
19
While this
chemical control of the physicochemical properties translates to
other metals,
20,21
it has proven to be particularly useful in
developing Ru-based dyes that are capable of generating high
power conversion efficiencies in the dye-sensitized solar cell
22
(DSSC).
13,523
Bis-tridentate Ru(II) complexes bearing a cyclometalating
ligand (e.g., pbpy = 6-phenyl-2,2-bipyridine) have a rich history
in the literature that extends back to the early work of
Constable et al.
24
and Sauvage et al.
25
We recently added to this
catalogue a series of cyclometalated Ru(II) complexes bearing
triphenylamine (TPA) units (e.g., Figure 1d) to augment light
absorption and enhance excited-state charge separation.
7,26,27
While these features had been previously observed for
polypyridyl Ru(II) architectures,
2831
the optical properties
and thermodynamic energy levels of the frontier molecular
orbitals of the cyclometalated derivatives are better positioned
for sensitizing TiO
2
.
7
Indeed, the high performance of these
dyes in the DSSC was made possible by recognizing that the
TPA and metal act as electrochemically isolated units in the
ground state, thus enabling a desirable energy level gradient
where the HOMO is confined to the TPA unit.
These promising results provided the impetus to further
develop the chemistry of the TPA-substituted platform
highlighted in Figure 1d. We therefore set out to investigate
the syntheses and properties of complexes containing alkyl
substituents on the TPA groups (25; Chart 1) in accordance
with a well-documented approach for improving the power
output and stability of the DSSC that involves placing
hydrophobic groups on one of the bidentate polypyridyl
ligands (Figure 1a and 1b).
34,35
The purported sensitivity of
dye regeneration by electrolytes to chalcogenides on the metal
complex also prompted us to develop a series where thiolates
and alkoxy groups are positioned about the TPA unit.
36
This
article also addresses how the position of the anionic ring
relative to the TPA unit (e.g., 2 vs 4; Chart 1) affects the optical
and electrochemical properties. The syntheses and physical
properties of these complexes are described herein and set the
stage for studying the light-absorption and charge-separation
events of bichromic cyclometalated complexes in future studies.
EXPERIMENTAL SECTION
Physical Methods. Elemental analysis (EA), electrospray ioniza-
tion mass spectrometry (ESI-MS), and electron impact (EI) mass
spectrometry data were collected at the Chemistry Instrumentation
Facility of the University of Calgary. Electrochemical measurements
were performed under anaerobic conditions with a Princeton Applied
Research VersaStat 3 potentiostat using dry solvents, a glassy carbon
Received: August 14, 2011
Published: January 13, 2012
Article
pubs.acs.org/IC
2012 American Chemical Society 1501 dx.doi.org/10.1021/ic201768e | Inorg. Chem. 2012, 51, 15011507
working electrodes, a Pt wire counter electrode, a Ag pseudoreference
electrode, and 0.1 M NBu
4
BF
4
MeCN supporting electrolyte solutions.
Electronic spectroscopic data were collected on MeCN solutions
collected using a Cary 5000 UVvis spectrophotometer (Varian).
Routine
1
H and
13
C NMR spectra were recorded at 400 and 100 MHz,
respectively, on a Bruker AV 400 instrument at ambient temperature.
Chemical shifts () are reported in parts per million (ppm) from low
to high field and referenced to residual nondeuterated solvent.
Standard abbreviations indicating multiplicity are used as follows: s =
singlet; d = doublet; t = triplet; m = multiplet. All proton assignments
correspond to the generic molecular schemes that are provided
(Figure 2).
Preparation of Compounds. All reactions and manipulations
were performed using solvents passed through an MBraun solvent
purification system prior to use. All reagents were purchased from
Aldrich and used without further purification except for RuCl
3
3H
2
O
(Pressure Chemical Company) and trimethyl-4,4,4-tricarboxylate-
2,2:6,2-terpyridine (Me
3
tctpy (L6); Helio Chemical Co., Switzer-
land). Purification by column chromatography was carried out using
silica (Silicycle, Ultrapure Flash Silica). Analytical thin-layer
chromatography (TLC) was performed on aluminum-backed sheets
precoated with silica 60 F254 adsorbent (0.25 mm thick; Merck,
Germany) and visualized under UV light. Organic and inorganic
compounds 4-(hexyloxy)-N-(4-(hexyloxy)phenyl)-N-(4-(4,4,5,5-tetra-
methyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (P1),
37
4-(5-bromo-2-
thienyl)-2,2:6,2-terpyridine (P3),
38
4-(5-bromothiophen-2-yl)-6-
phenyl-2,2-bipyridine (P4),
26
dimethyl 6-phenyl-2,2-bipyridine-4,4-
dicarboxylate (L7H),
5
Ru(P3)Cl
3
,
38
Ru(L6)Cl
3
,
39
and 1
7
were
prepared according to literature procedures. The experimental
procedures for preparation of 4-(hexylthio)-N-(4-(hexylthio)phenyl)-
N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (P2)
and its precursors (P2b and P2bc) and the ligands L2HL4H are
provided as Supporting Information.
[Ru(P4)(L6)]NO
3
(C1). A 250-mL round-bottom flask (RBF)
containing Ru(L6)Cl
3
(0.200 g, 0.33 mmol) and 4-(5-bromothiophen-
2-yl)-6-phenyl-2,2-bipyridine (P4) (0.141 g, 0.36 mmol) was charged
with a 120 mL of MeOH/H
2
O (5:1 v/v) solution containing 0.5 mL
of n-ethylmorpholine and then left at reflux for 14 h. After the reaction
was cooled, AgNO
3
(0.166 g, 0.98 mmol) was added and the reaction
mixture was set to reflux for an additional 2 h. The hot solution was
filtered, and the solvent was removed in vacuo. The residue was
purified by column chromatography [SiO
2
, acetone/MeOH, 8:1; R
f
=
0.50] to yield 0.252 g (80.6%) of the product as a dark black
microcrystalline solid.
1
H NMR (400 MHz, CDCl
3
): = 9.13 (s, 2H,
Figure 1. Listing of representative high-performance DSSC dyes that
contain anionic (a) monodentate,
32,33
(b) bidentate,
1
and (c, d)
tridentate ligands.
7,23
A common approach for improving the
performance of bidentate Ru-based dyestuff in the DSSC is to install
alkylated thiophenes at the R site.
34
The bichromic scaffold that serves
as the foundation of this study is highlighted by the enclosure.
7,26
Chart 1. Designation of Complexes and Ligands
a
a
Counterion = NO
3
for 1 and 2 and HCO

3
for 35. Proximal and

distal are relative to the TPA unit.
Figure 2. Generic labeling scheme for
1
H NMR signal assignments.
Inorganic Chemistry Article
dx.doi.org/10.1021/ic201768e | Inorg. Chem. 2012, 51, 15011507 1502
H
E
), 9.07 (d, 1H,
3
J = 7.9 Hz, H
d
), 9.03 (s, 1H, H
e
), 8.90 (d, 2H,
4
J =
1.7 Hz, H
D
), 8.09 (d, 1H,
4
J = 1.4 Hz, H
m
), 8.07 (d, 1H,
3
J = 3.9 Hz,
H
f
), 7.93 (t, 1H,
3
J = 6.4 Hz, H
c
), 7.74 (d, 1H,
3
J = 7.8 Hz, H
n
), 7.72
(d, 2H,
3
J = 5.9 Hz, H
A
), 7.65 (d, 2H,
3
J = 5.9 Hz, H
B
), 7.28 (d, 1H,
3
J
= 4.0 Hz, H
g
), 7.15 (d, 1H,
3
J = 5.1 Hz, H
a
), 7.02 (ddd, 1H,
3
J = 7.4,
3
J
= 5.4,
4
J = 0.9 Hz, H
b
), 6.67 (t, 1H,
3
J = 7.5 Hz, H
o
), 6.46 (t, 1H,
3
J =
7.4 Hz, H
p
), 5.34 (d, 1H,
3
J = 7.5 Hz, H
q
), 4.20 (s, 3H, H
F
), 3.94 (s,
6H, H
C
). HRMS (ESI): m/z = 894.0083 [(M)
+
] (calcd for
C
4 1
H
2 9
N
5
O
6
RuS
+
, m/z = 894. 0098). Anal . Cal cd f or
C
41
H
29
N
6
O
9
RuS2H
2
O: C, 49.41; H, 3.33; N, 8.41. Found: C,
49.80; H, 3.29; N, 8.09.
[Ru(L2)(L6)]NO
3
(2). To a 100-mL RBF containing C1 (0.160 g,
0.17 mmol) and 4-(hexyloxy)-N-(4-(hexyloxy)phenyl)-N-(4-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (P1) (0.100 g, 0.17
mmol) was added 25 mL of anhydrous DMF. After the mixture was
sparged with N
2
for 20 min, K
2
CO
3
(0.230 g, 1.66 mmol) and
Pd(PPh
3
)
4
(0.020 g, 0.02 mmol) were added and left to stir for 20 h at
70 C. The solvent was removed in vacuo, leaving a residue that was
dissolved in CH
2
Cl
2
. The white precipitate (K
2
CO
3
) was removed by
filtration, and the solvent was removed in vacuo. The residue was
2
f
=
microcrystalline solid. The yield was decreased due to formation of the
saponified product, [Ru(L2)(Me
2
tctpy)], (Me
2
tctpy = dimethyl-
4,4,4-tricarboxylate-2,2:6,2-terpyridine).
1
H NMR (400 MHz,
CDCl
3
): = 9.13 (s, 2H, H
E
), 8.99 (d, 1H,
3
J = 8.2 Hz, H
d
), 8.96
(s, 1H, H
e
), 8.91 (s, 2H, H
D
), 8.21 (s, 1H, H
m
), 8.17 (d, 1H,
3
J = 3.9
Hz, H
f
), 7.97 (t, 1H,
3
J = 7.0 Hz, H
c
), 7.78 (d, 1H,
3
J = 7.9 Hz, H
n
),
7.73 (d, 2H,
3
J = 5.9 Hz, H
A
), 7.65 (dd, 2H,
3
J = 5.9,
4
J = 1.6 Hz, H
B
),
7.51 (d, 2H,
3
J = 8.7 Hz, H
h
), 7.40 (d, 1H,
3
J = 3.9 Hz, H
g
), 7.19 (d,
1H,
3
J = 5.4 Hz, H
a
), 7.08 (d, 4H,
3
J = 8.8 Hz, H
j
), 7.05 (t, 1H,
3
J = 6.4
Hz, H
b
), 6.95 (d, 2H,
3
J = 8.7 Hz, H
i
), 6.85 (d, 4H,
3
J = 8.9 Hz, H
k
),
6.77 (t, 1H,
3
J = 7.7 Hz, H
o
), 6.46 (t, 1H,
3
J = 7.5 Hz, H
p
), 5.34 (d, 1H,
3
J = 7.5 Hz, H
q
), 4.20 (s, 3H, H
F
), 3.95 (s, 6H, H
C
), 3.94 (t, 4H,
3
J =
6.6 Hz, H
r
), 1.811.74 (m, 4H, H
s
), 1.501.42 (m, 4H, H
t
), 1.36
1.32 (m, 8H, H
u
, H
v
), 0.90 (t, 6H,
3
J = 7.0 Hz, H
w
). HRMS (ESI): m/z
= 1265.3768 [(M)
+
] (calcd for C
71
H
67
N
6
O
8
RuS
+
, m/z = 1265.3798).
Anal. Calcd for C
71
H
67
N
7
O
11
RuSH
2
OMeOH: C, 62.78; H, 5.34; N,
7.12. Found: C, 62.46; H, 5.19; N, 6.76.
[Ru(L3)(L6)]HCO
3
0.16 mmol) and 4-(hexylthio)-N-(4-(hexylthio)phenyl)-N-(4-(4,4,5,5-
sparged with N
2
for 20 min, K
2
CO
3
(0.217 g, 1.57 mmol) and
Pd(PPh
3
)
4
dissolved in CH
2
Cl
2
2
CO
3
) was removed by
2
, CH
2
Cl
2
/MeOH, 9:1; R
f
=
microcrystalline solid. The low yield is due to formation of the
saponified product, [Ru(L3)(Me
2
tctpy)].
1
H NMR (400 MHz,
CDCl
3
): = 9.60 (d, 1H,
3
J = 8.2 Hz, H
d
), 9.39 (s, 1H, H
e
), 9.12
(s, 2H, H
E
), 8.90 (s, 2H, H
D
), 8.66 (d, 1H,
3
J = 3.9 Hz, H
f
), 8.20 (s,
1H, H
m
), 8.02 (t, 1H,
3
J = 7.2 Hz, H
c
), 7.77 (d, 1H,
3
J = 7.7 Hz, H
n
),
7.73 (d, 2H,
3
J = 5.9 Hz, H
A
), 7.64 (dd, 2H,
3
J = 5.9,
4
J = 1.7 Hz, H
B
),
7.59 (d, 2H,
3
J = 8.6 Hz, H
h
), 7.46 (d, 1H,
3
J = 3.9 Hz, H
g
), 7.307.23
(m, 5H, H
a
, H
k
), 7.147.03 (m, 7H, H
j
, H
b
, H
i
), 6.76 (t, 1H,
3
J = 7.1
Hz, H
o
), 6.45 (t, 1H,
3
J = 7.4 Hz, H
p
), 5.31 (d, 1H,
3
J = 7.0 Hz, H
q
),
4.19 (s, 3H, H
F
), 3.94 (s, 6H, H
C
), 2.88 (t, 4H,
3
J = 7.3 Hz, H
r
), 1.68
1.60 (m, 4H, H
s
), 1.431.38 (m, 4H, H
t
), 1.301.23 (m, 8H, H
u
, H
v
),
0.87 (t, 6H,
3
J = 6.9 Hz, H
w
). HRMS (ESI): m/z = 1291.3345 [(M)
+
]
(calcd for C
71
H
67
N
6
O
6
RuS
3
+
, m/z = 1291.3360). Anal. Calcd for
C
72
H
68
N
6
O
9
RuS
3
4H
2
O: C, 60.45; H, 5.35; N, 5.87. Found: C, 60.45;
H, 4.94; N, 5.65.
[Ru(P3)(L7)]NO
3
(C2). A 250-mL RBF containing Ru(P3)Cl
3
(0.424 g, 0.71 mmol) and dimethyl 6-phenyl-2,2-bipyridine-4,4-
dicarboxylate (L7H) (0.234 g, 0.67 mmol) was charged with 120 mL
of a MeOH/H
2
O (5:1 v/v) solution containing 0.5 mL of n-
ethylmorpholine and then left at reflux for 14 h. After the reaction was
cooled, AgNO
3
(0.359 g, 2.12 mmol) was added and the reaction
mixture was set to reflux for an additional 2 h. The hot solution was
filtered, and the solvent was removed in vacuo. The residue was
2
, CH
2
Cl
2
/MeOH, 9:1; R
f
=
microcrystalline solid.
1
H NMR (400 MHz, CDCl
3
): = 8.89 (s, 1H,
H
D
), 8.84 (s, 2H, H
e
), 8.82 (s, 1H, H
E
), 8.658.63 (m, 3H, H
G
, H
d
)
8.15 (d, 1H,
3
J = 4.0 Hz, H
f
), 7.87 (d, 1H,
3
J = 7.8 Hz, H
H
), 7.81 (d,
1H,
3
J = 5.2 Hz, H
A
), 7.767.69 (m, 3H, H
c
, H
B
), 7.28 (d, 1H,
3
J =
3.86 Hz, H
g
), 7.09 (d, 2H,
3
J = 4.7 Hz, H
a
), 6.91 (t, 2H,
3
J = 6.0 Hz,
H
b
), 6.86 (t, 1H,
3
J = 6.8 Hz, H
I
), 6.66 (t, 1H,
3
J = 7.3 Hz, H
J
), 5.98 (d,
1H,
3
J = 6.5 Hz, H
K
), 4.18 (s, 3H, H
F
), 3.96 (s, 3H, H
C
). HRMS (ESI):
m/z = 842.0007 [(M)
+
] (calcd for C
39
H
27
BrN
5
O
4
RuS
+
, m/z =
842.0010). Anal. Calcd for C
39
H
27
BrN
6
O
7
RuS2H
2
O: C, 49.79; H,
3.32; N, 8.49. Found: C, 49.39; H, 3.04; N, 8.59.
[Ru(L4)(L7)]HCO
3
0.11 mmol) and 4-(hexyloxy)-N-(4-(hexyloxy)phenyl)-N-(4-(4,4,5,5-
sparged with N
2
for 20 min, K
2
CO
3
(0.153 g, 1.11 mmol) and
Pd(PPh
3
)
4
dissolved in CH
2
Cl
2
2
CO
3
) was removed by
2
f
=
saponified product, [Ru(L4)(ph-Medcbpy)] (ph-Medcbpy = methyl
6-phenyl-2,2-bipyridine-4,4-dicarboxylate).
1
H NMR (400 MHz,
CDCl
3
): = 8.96 (s, 2H, H
e
), 8.87 (s, 1H, H
D
), 8.81 (s, 1H, H
E
),
8.79 (d, 2H,
3
J = 8.2 Hz, H
d
), 8.64 (s, 1H, H
G
), 8.51 (d, 1H,
3
J = 3.9
Hz H
f
), 7.84 (d, 1H,
3
J = 7.7 Hz, H
H
), 7.73 (t, 2H,
3
J = 7.7 Hz, H
c
),
7.697.65 (m, 2H, H
A
, H
B
), 7.42 (d, 2H,
3
J = 8.7 Hz, H
h
), 7.27 (d, 1H,
3
J = 3.9 Hz, H
g
), 7.077.05 (m, 6H, H
a
, H
j
), 6.916.88 (m, 4H, H
b
,
H
i
), 6.856.79 (m, 5H, H
k
, H
I
), 6.63 (t, 1H,
3
J = 7.5 Hz, H
J
), 6.00 (d,
1H,
3
J = 7.5 Hz, H
K
), 4.15 (s, 3H, H
F
), 3.94 (s, 3H, H
C
), 3.92 (t, 4H,
3
J
= 6.6 Hz, H
r
), 1.791.72 (m, 4H, H
s
), 1.481.41 (m, 4H, H
t
), 1.36
1.30 (m, 8H, H
u
, H
v
), 0.89 (t, 6H,
3
J = 7.0 Hz, H
w
). HRMS (ESI): m/z
= 1207.3742 [(M)
+
] (calcd for C
69
H
65
N
6
O
6
RuS
+
, m/z = 1207.3742).
Anal. Calcd for C
70
H
66
N
6
O
9
RuS3H
2
O: C, 63.67; H, 5.49; N, 6.35.
Found: C, 64.01; H, 5.45; N, 6.40.
[Ru(L5)(L7)]HCO
3
0.18 mmol) and 4-(hexylthio)-N-(4-(hexylthio)phenyl)-N-(4-(4,4,5,5-
sparged with N
2
for 20 min, K
2
CO
3
(0.250 g, 1.81 mmol) and
Pd(PPh
3
)
4
dissolved in CH
2
Cl
2
2
CO
3
) was removed by
2
, CH
2
Cl
2
/MeOH, 9:1; R
f
=
saponified product, [Ru(L5)(ph-Medcbpy)].
1
H NMR (400 MHz,
CDCl
3
): = 9.02 (s, 2H, H
e
), 8.888.81 (m, 4H, H
D
, H
E
, H
d
), 8.64 (s,
1H, H
G
), 8.61 (d, 1H,
3
J = 3.9 Hz, H
f
), 7.85 (d, 1H,
3
J = 7.5 Hz, H
H
),
7.747.66 (m, 4H, H
A
, H
B
, H
c
), 7.53 (d, 2H,
3
J = 8.6 Hz, H
h
), 7.39 (d,
1H,
3
J = 3.9 Hz, H
g
), 7.23 (d, 4H,
3
J = 8.6 Hz, H
k
), 7.047.00 (m, 8H,
H
a
, H
i
, H
j
), 6.90 (t, 2H,
3
J = 6.3 Hz, H
b
), 6.82 (t, 1H,
3
J = 7.2 Hz, H
I
),
6.64 (t, 1H,
3
J = 7.2 Hz, H
J
), 6.00 (d, 1H,
3
J = 7.2 Hz, H
K
), 4.16 (s,
3H, H
F
), 3.94 (s, 3H, H
C
), 2.87 (t, 4H,
3
J = 7.4 Hz, H
r
), 1.671.60 (m,
4H, H
s
), 1.451.38 (m, 4H, H
t
), 1.311.26 (m, 8H, H
u
, H
v
), 0.87 (t,
6H,
3
J = 6.8 Hz, H
w
). HRMS (ESI): m/z = 1239.3249 [(M)
+
] (calcd
for C
69
H
65
N
6
O
4
RuS
3
+
, m/z = 1239.3290). Anal. Calcd for
C
70
H
66
N
6
O
7
RuS
3
3H
2
O: C, 62.07; H, 5.36; N, 6.20. Found: C,
62.09; H, 4.96; N, 6.50.
RESULTS AND DISCUSSION

This study details the syntheses and physicochemical properties
of four new cyclometalated Ru(II) complexes bearing hydro-
phobic TPA substituents (Chart 1 and Table 1). The ensuing
sections will address, in sequence, (i) a synthetic protocol for
installing aliphatic groups on the TPA substituent, (ii) the
benefit of placing the TPA on the neutral chelating ligand
rather than the anionic ligand, and (iii) the role that terminal
O-hexyl and S-hexyl substituents have on the physicochem-
ical properties.
Synthetic Protocol for Installing the Aliphatic Groups.
The Suzuki reagent P1 was synthesized according to
documented methodologies.
37
Attempts to synthesize the
thiolate-substituted TPA units P2b and P2c by similar methods
proved unsuccessful. An alternative route stemming from a
literature procedure
40
provided access to the boronic ester P2
(Scheme S1, Supporting Information). Reagents (P1 and/or
P2) could then be coupled to the appropriate chelating ligands
(P3 and/or P4) via Suzuki cross-coupling methods to furnish
the hydrophobic TPA-functionalized tridentate ligands L2H,
L3H, and L4 in high yields (Scheme S2, Supporting
Information). The seemingly trivial task of binding these
ligands to the Ru center, however, was made difficult by the
inherently poor solubility of the ligands in polar media being in
discord with the need for a high dielectric solvent (e.g.,
MeOH/H
2
O 5:1 v/v) to induce halide displacement and
cyclometalation.
41
While the solubility of TPA-appended pbpy
ligands can be enhanced with a small amount of THF (e.g.,
MeOH/H
2
O/THF 5:1:1 v/v/v
7,26
), the long alkyl chains of
L2H and L3H demanded a greater fraction of THF, thus
yielding a mixture of cyclometalated/noncyclometalated
products that were not easily separated by column chromatog-
raphy (Figure 3; Route A). We also tried to carry out the
cyclometalation step with L2H and [Ru(C
6
H
6
)Cl
2
]
2
prior to
chelation of the Me
3
tctpy (L6) ligand;
3
but this strategy proved
unsuccessful with myriad solvent combinations at variable
temperatures (Figure 3; Route B).
With the aforementioned synthetic routes exhausted, we
turned our attention to less conventional cross-coupling
reactions involving the bis-tridentate Ru coordination complex
(Figure 3; Route C).
42
This approach, which proved to be
remarkably facile, involved the chelation of pro-ligand P4
7
to
Ru(L6)Cl
3
to furnish the brominated precursor complex C1,
which, in turn, was reacted with Suzuki reagents P1/P2 in
anhydrous basic DMF to yield 2 and 3. Complexes 4 and 5
were prepared from C2 following a similar protocol. One
consequence of this synthesis was partial saponification of the
product (i.e., one of the methylesters could be converted into
the corresponding carboxylic acid derivative); however, these
two products could be readily separated by column
chromatography. While 1 is soluble in a wide range of organic
solvents (e.g., CH
2
Cl
2
, CHCl
3
, MeOH, EtOH, DMF, DMSO),
the complexes bearing the long aliphatic chains about the TPA
unit were significantly more soluble in less polar solvents (e.g.,
THF).
In overcoming a major synthetic roadblock, we were able to
isolate and fully characterize the redox and spectroscopic
properties of pure phases of the title complexes. The inherent
asymmetry of each of the complexes enables an accurate
assignment of the aromatic signals by
1
H NMR (1D and 2D)
spectroscopy. Sample purity was verified by mass spectrometry
Table 1. Summary of Spectroscopic and Electrochemical
Properties for Complexes C1C2 and 15
UVvis absorbance data (nm)
a
E
1/2
ox
(V vs NHE)
b
compound
max
( 10
3
M
1
cm
1
)
Ru(III)/
Ru(II)
TPA
+
/
TPA
0
C1 523 (21.1), 431 (29.5),
327 (53.0)
1.03 c
1 524 (34.5), 435 (42.3),
330 (48.4)
1.03 0.93
2 526 (34.4), 435 (44.5),
330 (48.4)
1.04 0.92
3 526 (28.0), 432 (40.0),
327 (54.7)
1.03 1.03
C2 561 (25.3), 389 (18.4) 0.89 c
4 572 (36.0), 421 (38.1) 0.87 0.95
5 571 (32.2), 418 (36.7) 0.87 1.05
a
Data collected in MeCN; values indicated in parentheses with units
of 10
3
M
1
cm
1
; shoulders at ca. 690 nm and select high-energy
maxima are not listed.
b
Data collected using 0.1 M NBu
4
BF
4
MeCN
solutions at 100 mV/s and referenced to a [Fc]/[Fc]
+
internal
standard followed by conversion to NHE; [Fc]/[Fc
+
] = +640 mV vs
NHE in MeCN.
c
Not observed.
Figure 3. Synthetic pathways used to isolate 25 (Route C). Route A produced an inseparable byproduct, and Route B did not yield the desired
product. Reaction conditions: (a) AgNO
3
, n-ethylmorpholine, MeOH/H
2
O/THF (5:1:>1, v/v/v), reflux, 16 h; (b) KPF
6
, NaOH, MeCN, 40 C, 18
h; (c) desired product was not generated in a variety of solvents (i.e., MeOH, EtOH, MeCN, CH
2
Cl
2
, CHCl
3
, CCl
4
, DMF, DMSO,
OHCH
2
CH
2
OH); (d) AgNO
3
, n-ethylmorpholine, MeOH/H
2
O (5:1, v/v/v), reflux, 16 h; (e) K
2
CO
3
, Pd(PPh
3
)
4
, DMF, 70 C, 20 h.
and elemental analyses. We note that many of the complexes
contain waters of hydration.
A full assessment of the electrochemical and spectroscopic
data recorded in MeCN was augmented by the extensive
catalogue of compounds reported in our previous studies.
7,26
The broad and intense absorption profiles of related
compounds have been previously shown to arise from
overlapping metal-to-ligand charge-transfer (MLCT) and
intraligand charge-transfer (ILCT) absorption bands.
7
For
complexes containing L6, for example, the lower energy MLCT
bands (i.e., shoulder at 580 nm and maximum at 520 nm)
involve promotion of an electron from metal-based orbitals that
are delocalized over the anionic ring of the chelating ligand to
the * orbital of the neutral chelating ligand; the higher energy
bands (e.g., 431 nm) arise from MLCT transitions involving
the * network of the cyclometalating ligand. A comparison of
the spectra of C1 and 2 illustrates explicitly how the TPA unit
enhances light absorption (Figure S1, Supporting Information),
and provides confirmation that the absorption bands in
bichromic complexes of this type are both MLCT and ILCT
in character.
7,26
The low-energy ILCT transitions emanating
from the TPA unit involve excited-state character on the *
system of the adjacent chelating ligand. Introduction of long
alkyl chains has a negligible effect on the spectroscopic
properties of the complexes (e.g., 1 vs 2; Figure S1a,
Supporting Information). Note that the absorption traces of
C1 and 2 extend beyond 800 nm regardless of whether a TPA
unit is present. We assign the low-energy shoulder centered at
690 nm to direct population of the
3
MLCT state facilitated by
the heavy Ru atom.
43
Cyclic voltammograms of 1 and 2 reveal two distinctive and
quasi-reversible oxidation processes (Figure S1, Supporting
Information). The first process corresponds to oxidation of the
TPA unit (i.e., E
1/2
, TPA
+
/TPA
0
+0.9 V vs NHE) with a
closely spaced Ru(III)/Ru(II) redox couple at +1.0 V vs NHE
for both 1 and 2.
7,44,45
Note that the cyclic voltammograms of
complexes C1 and 2 (Figure S1b, Supporting Information)
indicate a lack of communication between the two redox-active
sites on the basis of the static Ru(III)/Ru(II) couple remains
static (i.e., +1.03 V vs NHE).
7,26
The length of the alkyl
chains has a negligible effect on the optical and electrochemical
properties. The assignment of the redox waves observed in the
cyclic voltammetry experiments was aided by previous studies
and spectroelectrochemical experiments (Figure S3, Supporting
Information). Upon application of a fixed potential of +0.95 V
vs NHE (which is not expected to oxidize the Ru(II) center),
several changes are observed in the absorption spectrum. In
particular, growth of the low-energy absorption band centered
at 750 nm is attributed to a radical species 2
2+
, which is the
product of a one-electron oxidation of 2
+
.
30,46
This absorption
band is specifically assigned to a species where the radical is
localized to the TPA fragment of the complex.
Position of the Organometallic Bond. We previously
demonstrated that the anionic ring of dyes related to 1 should
be in the flanking position of the chelating ligand to engender
optical and electrochemical properties appropriate for sensitiz-
ing n-type semiconductors.
7,26
A point we did not explicitly
address in these studies, however, is whether the phenyl ring
should be on the chelating ligand attached to the TPA unit as
opposed to the adjacent chelate. (Note that the latter scheme
was recently reported
5
). While we situated the TPA on the
cyclometalating ligand to leave all three acid modalities on
4,4,4-tricarboxylate-2,2:6,2-terpyridine (tctpy) accessible for
binding to TiO
2
, only two acid groups are, in principle, needed
for binding and electron injection.
47
Thus, we include in this
study a synthetic route to furnish derivatives where the TPA
groups are attached to the neutral chelate (e.g., 4 and 5;
Scheme S1, Supporting Information). An attractive feature of
this particular arrangement is that the anionic ring is trans to
the pyridine containing the (potential) anchoring groups to
potentially promote more efficient electron injection.
48
More-
over, 4 and 5 do not contain the Me
3
tctpy ligand, which
currently stands as an expensive component of commercial
DSSC dyes.
The protocol used to prepare 2 and 3 also worked effectively
in preparing 4 and 5, thereby demonstrating the versatility of
using CC cross-coupling methodologies to attach the
aliphatic TPA unit to the coordinatively saturated metal
complexes. The
1
H NMR spectra of 24 reveal a clear
response of chemical shifts to the position of the RuC bond
(Figure 4). Confirmation of cyclometalation by the pbpy
chelate is provided in the form of the distinctively upfield shift
of the proton ortho to the RuC bond (i.e., H
q
and H
K
for 2
and 4, respectively). The H
K
resonance of 4 is downfield
relative to that of H
q
for 2 due to the electron-withdrawing
CO
2
Me group being trans to the anionic phenyl ring.
Figure 5 illustrates how the position of the organometallic
bond affects the optical properties. The low-energy shoulder in
Figure 4.
1
H NMR spectra for CDCl
3
solutions of 24 at ambient
temperatures highlighting how the terminal substitutents and the
position of the RuC bond affect the proton resonances. Color
scheme: green = H
k
; red = H
r
; blue = H
q
/H
K
; purple = H
j
; dashed
lines are provided to guide the reader.
2 (580 nm) becomes more pronounced in the case of 4,
which is notable in the collective pursuit of dyes that absorb at
the maximum of the solar flux at ca. 600 nm.
49
While it is
difficult to accurately discriminate how the position of the
organometallic bond affects the electrochemical properties
because of the disparate number of CO
2
Me groups for 2 and
4, the Ru(III)/Ru(II) redox couple does appear to be affected
to some extent because the +170 mV shift for 4 relative to 2
cannot be fully accounted for by a single CO
2
Me group (e.g.,
loss of two CO
2
Et groups has been shown to only affect the
Ru(III)/Ru(II) redox potential by +140 mV
3
). The TPA
oxidation potential is not significantly affected by the position
of the RuC bond in 2 and 4 (e.g., +0.92 and +0.95 V vs NHE
for 2 and 4, respectively), which is again consistent with the
metal and TPA units being electrochemically isolated in the
ground state.
7,26
Effect of Terminal Chalcogenide Substituents (O vs S)
on the TPA. Isolation of the alkoxy- and thiolate-substituted
TPAs was achieved following the aforementioned cross-
coupling schemes (Figure 3; Route C). An examination of
the
1
H NMR spectra of 2 and 3 indicate that the protons ortho
to the chalcogen on the TPA (e.g., H
k
) and the methylene
protons (i.e., H
r
) of the aliphatic chain are affected the most by
the different chalcogens about the TPA (Figure 4). The
divergence of the chemical shifts (i.e., H
k
and H
r
are shifted
downfield and upfield, respectively, for 2 relative to 3) indicates
that the larger S orbitals better shield the methylene protons
than the corresponding O atom of the alkoxy group but display
inferior orbital overlap with the system of the TPA unit.
Consequently, the S atom donates less electron density into the
system of the TPA relative to the O atom. Less electron
donation of the S atom into the aromatic system of the TPA
was authenticated by electrochemical measurements: the
TPA
+
/TPA
0
redox couple appears at +0.92 and +1.03 V vs
NHE for 2 and 3, respectively (Figure 5) (The Ru(III)/Ru(II)
redox couple was not affected). The different intensities of the
optical spectra for 2 and 3 (Figure 5) also appear to be manifest
in this electron donation into the aromatic systems of the TPA
units affecting the transition dipole of the ILCT transitions.
SUMMARY
The primary objective of this study was to develop a protocol
for isolating hydrophobic bichromic cyclometalated Ru(II)
complexes related to 1.
7,26
Functionalization of the TPA units
with aliphatic chains gave rise to a host of solubility issues that
rendered our previously established synthetic methodologies
unsuccessful. Fortunately, it was found that Pd-catalyzed CC
cross-coupling reactions between appropriately functionalized
bis-tridentate Ru metal complexes (C1 and C2) and TPA units
were remarkably efficient for making the target complexes. This
synthetic endeavor also enabled us to position the organo-
metallic bond within the scaffold of 1 from the ligand bearing
the TPA unit to the anchoring chelate. Not only does this
arrangement induce a bathochromically shifted absorption
envelope better matched to the incident solar flux but it also
sidesteps the use of the expensive tctpy ligand.
While the TPA unit is a common constituent in organic
DSSC dyes,
50,51
there is currently no example of an organic or
metal sensitizer where the TPA has been substituted with
thiolate groups. This observation prompted us to develop a
synthetic scheme for isolating Ru complexes bearing TPA units
that have been functionalized with thiolate groups. Character-
ization of these dyes, however, reveals that the thiolates are
weaker donors than the alkoxy groups because of the less
favorable orbital interactions with the phenyl rings of the TPA
group. This finding has consequences when inducing intra-
molecular charge transfer, namely, there will be a lower
thermodynamic driving force for the thiolate-substituted TPA
group to reduce the photo-oxidized metal fragment. Con-
sequently, we do not expect the sensitization of n-type
semiconductors with bichromic sensitizers bearing thiolate-
substituted TPA groups to be enhanced (if kinetic parameters
are held at parity). Studies are underway to verify this claim.
With the synthetic chemistry for bichromic cyclometalated
Ru(II) complexes now fully developed, future studies will focus
exclusively on probing the interaction between the chalcoge-
nide-substituted TPA units and the I
-based electrolyte species

in the DSSC. We are also evaluating whether the aliphatic
chains enhance the stability of these complexes in the DSSC as
they do with dyes bearing bidentate ligands (e.g., Z907
35
).
52
The device performance for this entire suite of complexes in
liquid-junction and solid-state DSSCs will be disseminated in
future studies.
ASSOCIATED CONTENT
*S Supporting Information
Synthetic schemes for P2 and ligands L2HL3H and L4 and
experimental details. This material is available free of charge via
the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: cberling@ucalgary.ca.
Figure 5. UVvis spectra and cyclic voltammograms of select
compounds in MeCN highlight the effect on the optical and
electrochemical properties upon (a) altering the position of the Ru
C bond (R
1
= -O-hex) and (b) substitution of the chalcogen (O vs S)
para to the N of the TPA.
ACKNOWLEDGMENTS
This work was financially supported by the Canadian Natural
Science and Engineering Research Council (NSERC), Canada
Research Chairs, Canadian Foundation for Innovation (CFI),
Alberta Ingenuity, and the Canada School of Energy and
Environment (CSEE). K.C.D.R. is grateful to NSERC and
Alberta Innovates for student fellowships. We thank Prof. Todd
Sutherland (University of Calgary) for access to spectroelec-
trochemical of equipment.
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Derivatization of Bichromic Cyclometalated Ru (II) Complexes With Hydrophobic Substituents

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RESULTS AND DISCUSSION

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