Syntheses and luminescence behaviour of dinuclear copper(I) selenolate and

tellurolate complexes. X-Ray crystal structures of [Cu

2
(m-dppm)
2
(m-SePh)]BF
4
and [Cu
2
(m-dppm)
2
(m-TePh)]BF
4
Vivian Wing-Wah Yam,* Chi-Ho Lam and Kung-Kai Cheung
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P.R. China
E-mail: wwyam@hku.hk
Received (in Cambridge, UK) 4th December 2000, Accepted 8th February 2001
First published as an Advance Article on the web 1st March 2001
A series of novel dinuclear copper(I) m-chalcogenolate
complexes is synthesized and their photophysics studied; the
X-ray crystal structures of [Cu
2
(m-dppm)
2
(m-SePh)]BF
4
and
[Cu
2
(m-dppm)
2
(m-TePh)]BF
4
are reported.
Increasing interest in the investigation of copper(I) complexes
with chalcogenide ligands has emerged.
1,2
The closely related
class of ligands, the chalcogenolates, has also attracted
enormous attention owing to their importance in biological
systems and their propensity to form metal complexes and
clusters of various bonding modes and structural motifs.
3
In
view of this and the ready functionalization of the chalcogeno-
late ligands via a change in the substituent on the heteroatom to
effect steric and electronic control of the ligating ability, it
would be of interest to synthesize and study the related copper(I)
chalcogenolate complexes. Compared with copper(I) thiolates,
reports on selenolate and tellurolate complexes are relatively
rare.
4
Moreover, the luminescence properties of copper(I)
chalcogenolate complexes are almost unexplored
5
and represent
a challenging area of research. Here we report the syntheses and
photophysics of a new class of dinuclear copper(I) chalcogeno-
lates and the X-ray crystal structures of [Cu
2
(m-dppm)
2
(m-
SePh)]BF
4
and [Cu
2
(m-dppm)
2
(m-TePh)]BF
4
.
Reaction of [Cu
2
(m-dppm)
2
(MeCN)
2
](BF
4
)
2
with the corre-
sponding sodium chalcogenolate (prepared in situ from the
diaryldiselenide or diarylditelluride and NaBH
4
) in a molar ratio
of 1+1 in THF and under anaerobic and anhydrous conditions
afforded dinuclear copper(I) m-chalcogenolate complexes,
[Cu
2
(m-dppm)
2
(m-EAr)]BF
4
(EAr = SePh 1, SeC
6
H
4
Cl-p 2,
TePh 3, TeC
6
H
4
Me-p 4) in ca. 1962% yield. Single crystals of
1 and 3 suitable for diffraction studies were grown by layering
of diethyl ether on concentrated solutions of the complexes in
acetone. All of the newly synthesized dinuclear copper(I)
complexes gave satisfactory elemental analyses, and have been
characterized by
1
H and
31
P NMR spectroscopy, and positive
FAB mass spectrometry. The X-ray crystal structures of
complexes 1 and 3 have also been determined.
Fig. 1 shows the perspective drawing of the complex cation of
3. The two copper atoms of the dinuclear complexes are held in
close proximity by three bridging ligands, two dppm ligands
acting through the P atoms and one chalcogenolate ligand acting
through the Se/Te atom. The Se/Te atom asymmetrically
bridges the two copper atoms, with the Cu(2)Se/Te distances
[1, Cu(2)Se(1) 2.485 ; 3, Cu(2)Te(1) 2.608 ] longer than
those of Cu(1)Se/Te [1, Cu(1)Se(1) 2.371 ; 3, Cu(2)Te(1)
2.532 ]. In addition, a short non-bonded contact of ca. 2.4
is observed between the Cu(2) atom of the complex cation and
an oxygen atom of the acetone solvent molecule, with a
tendency to afford a distorted trigonal bipyramidal arrangement
about Cu(2) [1, Cu(1)Cu(2)O(1) 150.5(3) with Cu(2)
deviated 0.43 towards O(1); 2, Cu(1)Cu(2)O(1)
153.7(3) with Cu(2) deviated 0.39 towards O(1)], while
Cu(1) assumes a distorted tetrahedral arrangement. It is noted
that the phenyl ring of the chalcogenolate is bent towards one
side of the Cu
2
E triangle (E = Se, Te) due to the sp
3
hybridization of the Se/Te atom. The Cu

Cu distances in 1 and
3 are in the range 2.7232.739 . They are shorter than the sum
of van der Waals radii for copper (2.8 )
6
and this may indicate
weak metalmetal interactions in the complexes.
The electronic absorption spectra for complexes 14 in
dichloromethane are characterized by absorption shoulders at
ca. 250 and 260295 nm (Table 1). Since the electronic
absorption spectra were rather featureless, no further attempts
were made to unambiguously assign the absorption bands. The
emission spectra of the dinuclear complexes 14 in degassed
acetone showed a low energy emission at ca. 600630 nm, with
emission energies in the order 4 ! 3 > 2 ! 1 (Table 1).
Complexes 3 and 4 with tellurolate ligands show slightly higher
emission energies than those with selenolate ligands 1 and 2.
Such an energy trend appears to depend upon the p-accepting
ability of the chalcogenolate ligand, in which the areneseleno-
late is a better p-acceptor ligand than the arenetellurolate. This
suggests that the low energy emission involves an excited state
Fig. 1 Perspective drawing of the complex cation of 3 with the atomic
numbering scheme. Hydrogen atoms have been omitted for clarity. Thermal
ellipsoids are shown at the 40% probability level. Selected bond distances
() and bond angles () for complex 3: Cu(1)Cu(2) 2.723(1), Cu(1)
Te(1) 2.532(1), Cu(2)Te(1) 2.608(1), Cu(1)P(1) 2.243(3), Cu(2)P(2)
2.283(3), Cu(2)O(1) 2.36(1); Te(1)Cu(1)P(1) 116.80(8), Te(1)Cu(2)
P(2) 112.40(8), Te(1)Cu(1)P(4) 112.44(9), Te(1)Cu(2)P(3) 111.01(8),
P(1)Cu(1)P(4) 129.3(1), P(2)Cu(2)P(3) 128.46(10), Cu(1)Te(1)
C(1) 110.7(3), Cu(2)Te(1)C(1) 107.1(3). Selected bond distances () and
bond angles () for complex 1: Cu(1)Cu(2) 2.739(2), Cu(1)Se(1)
2.371(2), Cu(2)Se(1) 2.485(2), Cu(1)P(1) 2.241(4), Cu(2)P(2) 2.296(3),
Cu(2)O(1) 2.39(1); Se(1)Cu(1)P(1) 118.3(1), Se(1)Cu(2)P(2)
112.91(10), Se(1)Cu(1)P(4) 111.1(1), Se(1)Cu(2)P(3) 108.9(1), P(1)
Cu(1)P(4) 129.0(1), P(2)Cu(2)P(3) 128.0(1), Cu(1)Se(1)C(1)
113.5(3), Cu(2)Se(1)C(1) 106.4(3).
This journal is The Royal Society of Chemistry 2001
DOI: 10.1039/b009676h Chem. Commun., 2001, 545546 545
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of metal-to-ligand charge transfer (MLCT) [Cu
2
? ER
2
]
origin. A related dinuclear copper(I) complex, [Cu
2
(m-
dppm)
2
(m-O
2
CMe)]
+
,
7
in which the lowest lying excited state
was suggested to be MLCT [copper ? phosphine/acetate] in
character, as supported by molecular orbital calculations, shows
a relatively high energy emission at ca. 470 nm. However, low
energy emissions at ca. 600630 nm are observed for
complexes 14 and the emission energy difference between the
dinuclear copper(I) selenolate and tellurolate complexes is
relatively small. This, together with the fairly short CuCu
contacts (ca. 2.7 ) found in these dinuclear complexes, may be
more suggestive of an assignment of the emission as having a
metal-centered ds/dp origin. Thus, the low energy emission in
the dinuclear copper(I) chalcogenolate complexes is tentatively
assigned as derived from an excited state that is predominantly
metal-centered ds/dp in origin, mixed with some MLCT [copper
?chalcogenolate/phosphine] character.
The cyclic voltammograms of complexes 14 show quasi-
reversible oxidation couples in the range 0.68 to 0.80 V vs. SCE
(Table 1). A relatively small shift in the potential of the
oxidation couples is observed. The oxidation couple is tenta-
tively assigned as a copper(I/II) metal-centered oxidation. No
reduction wave was observed even when the potential was
scanned to 22.4 V vs. SCE. Further oxidation and reduction of
the complexes resulted in decomposition, as suggested by the
irreversibility of the couples at higher anodic and cathodic
potentials.
V. W. W. Y. acknowledges financial support from the
Research Grants Council and The University of Hong Kong.
The receipt of a Croucher Senior Research Fellowship by
V. W. W. Y. from the Croucher Foundation is gratefully
acknowledged. C. H. L. acknowledges the receipt of a
postgraduate studentship, administered by The University of
Hong Kong.
Notes and references
Selected spectroscopic data for 1.
1
H NMR (300 MHz, acetone-d
6
, 298
K): d 3.6 (m, 4H, CH
2
), 6.67.6 (m, 45H, Ph);
31
P{
1
H} NMR (202 MHz,
acetone-d
6
, 298 K): d 26.3. Positive FAB-MS: m/z 1052 [M 2BF
4
]
+
. Calc.
for Cu
2
C
56
H
49
P
4
SeBF
4
: C, 59.21; H, 4.63; Found: C, 59.13; H, 4.75%. For
2.
1
H NMR (300 MHz, acetone-d
6
, 298 K): d 3.6 (m, 4H, CH
2
), 6.77.6 (m,
44H, Ph);
31
P{
1
H} NMR (202 MHz, acetone-d
6
, 298 K): d 25.9. Positive
FAB-MS: m/z 1088 [M 2 BF
4
]
+
. Calc. for Cu
2
C
56
H
48
P
4
SeClBF
4
.
CH
2
Cl
2
:
C, 54.42; H, 4.01; Found: C, 54.67; H, 3.96%. For 3:
1
H NMR (300 MHz,
CD
2
Cl
2
, 298 K): d 3.5 (m, 4H, CH
2
), 6.57.7 (m, 45H, Ph);
31
P{
1
H} NMR
(202 MHz, acetone-d
6
, 298 K): d 26.9. Positive FAB-MS: m/z 1102 [M 2
BF
4
]
+
. Calc. for Cu
2
C
56
H
49
P
4
TeBF
4
.
CH
2
Cl
2
: C, 53.81; H, 4.04; Found: C,
53.81; H, 3.97%. For 4.
1
H NMR (300 MHz, acetone-d
6
, 298 K): d 2.1 (s,
3H, CH
3
), 3.5 (m, 4H, CH
2
), 6.57.7 (m, 44H, Ph);
31
P{
1
H} NMR (202
MHz, acetone-d
6
, 298 K): d 26.8. Positive FAB-MS: m/z 1116 [M 2BF
4
]
+
.
Calc. for Cu
2
C
57
H
51
P
4
TeBF
4
.
CH
2
Cl
2
: C, 54.16; H, 4.15. Found: C, 54.36;
H, 4.05%.
Crystal data for [Cu
2
(m-dppm)
2
(m-SePh)]BF
4
1: [(C
56
H
49
P
4
SeCu
2
)
+
BF
4
2
(CH
3
)
2
CO(C
2
H
5
)
2
O], M
r
= 1270.96, orthorhombic, space group
P2
1
2
1
2
1
(no. 19), a = 13.539(3), b = 21.137(4), c = 21.223(4) , V =
6073(2)
3
, Z = 4, D
c
= 1.390 g cm
23
, m(Mo-Ka) = 14.59 cm
2l
, F(000)
= 2608, T = 301 K, using Mo-Ka radiation (l = 0.71073 ). 5305 unique
reflections were measured, of which 3923 reflections with I > 3s(I) were
used in the structural analysis. Convergence for 430 variable parameters by
least-squares refinement on F with w = 4F
o
2
/s
2
(F
o
2
), where s
2
(F
o
2
) =
[s
2
(I) + (0.024F
o
2
)
2
] for 3923 reflections with I > 3s(I) was reached at R
= 0.054 and wR = 0.071 with a goodness-of-fit of 2.98. For [Cu
2
(m-
dppm)
2
(m-TePh)]BF
4
3: [(C
56
H
49
P
4
TeCu
2
)
+
BF
4
2
(CH
3
)
2
CO
.
(CH
3
-
CH
2
)
2
O], M = 1319.60, orthorhombic, space group P2
1
2
1
2
1
(no. 19), a =
13.546(2), b = 21.094(3), c = 21.274(3) , V = 6078(1)
3
, Z = 4, D
c
=
1.442 g cm
23
, m(Mo-Ka) = 13.29 cm
2l
, F(000) = 2680, T = 301 K, using
Mo-Ka radiation (l = 0.71073 ). 6114 unique reflections were obtained
from a total of 32593 measured reflections (R
int
= 0.056). 4642 reflections
with I > 3s(I) were used in the structural analysis. Convergence for 624
variable parameters by least-squares refinement on F with w = 4F
o
2
/
s
2
(F
o
2
), where s
2
(F
o
2
) = [s
2
(I) + (0.034F
o
2
)
2
] for 4742 reflections with I
> 3s(I) was reached at R = 0.055 and wR = 0.072 with a goodness-of-fit
of 2.09. CCDC 155745 and 155746. See http://www.rsc.org/suppdata/cc/
b0/b009676h/ for crystallographic files in .cif or other electronic format.
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Table 1 Photophysical and electrochemical data of complexes 14
Emission
b
Complex
Absorption,
a
l/nm (e
max
/
dm
3
mol
21
cm
21
) Medium (T/K) l
em
/nm (t
o
/ms)
Oxidation,
d,e
E
1/2
(V vs.
SCE)
1 286sh (21 850) Acetone (298) 630 (6.0)
c
+0.68
Solid (298) 431, 452 ( < 0.1)
2 266sh (34 290), Acetone (298) 626 ( < 0.1)
c
+0.70
296sh (31480) Solid (298) 440, 468sh ( < 0.1)
3 256sh (42 380) Acetone (298) 607 ( < 0.1)
c
+0.79
Solid (298) 439, 464sh ( < 0.1)
4 256sh (40 530) Acetone (298) 601 ( < 0.1)
c
+0.80
Solid (298) 438, 463sh ( < 0.1)
a
In CH
2
Cl
2
.
b
Excitation wavelength at 350 nm.
c
Excitation wavelength at 370
nm.
d
In MeCN (0.1 M
n
Bu
4
NPF
6
), glassy carbon electrode, scan rate 100
mV s
21
, 298 K.
e
E
1/2
is taken to be the average of E
pa
and E
pc
, where E
pa
and
E
pc
are the anodic and cathodic peak potentials of the quasi-reversible couple,
respectively.
546 Chem. Commun., 2001, 545546
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