Structure and emission properties of mixed-ligand Cu(I) complexes containing phosphinesulfide ligands

Article abstract of DOI:10.1016/j.poly.2009.05.041

Mixed-ligand Cu(I) complexes containing phosphinesulfide ligands were synthesized, and the structure and emission properties were studied for the Cu(I) complexes. X-ray crystallographic study showed that a chelating phosphinesulfide and diimine are coordi

Full text of DOI:10.1016/j.poly.2009.05.041

Polyhedron 28 (2009) 2730–2734
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Structure and emission properties of mixed-ligand Cu(I) complexes containing
phosphinesulfide ligands
*
*
Ayumi Dairiki, Toshiaki Tsukuda , Kenji Matsumoto, Taro Tsubomura
Department of Materials and Life Science, Seikei University, 3-3-1 Kichijoji-Kitamachi Musashino, Tokyo 1808633, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Mixed-ligand Cu(I) complexes containing phosphinesulfide ligands were synthesized, and the structure
and emission properties were studied for the Cu(I) complexes. X-ray crystallographic study showed that
a chelating phosphinesulfide and diimine are coordinated to Cu(I) center. Coordination geometry around
Cu(I) center of each complex is described as a distorted tetrahedron. Some of the complexes show pho-
toluminescence in the solid state.
Received 9 January 2009
Accepted 13 May 2009
Available online 27 May 2009
Keywords:
Phosphinesulfide
Diimine
Ó 2009 Elsevier Ltd. All rights reserved.
Cu(I) complexes
Mixed-ligand complexes
X-ray crystallography
Emission properties
MLCT transition
1. Introduction
used as the alternatives of phosphine ligands (Fig. 1). Several
Cu(I) complexes with phosphine sulfides have been reported
Much attention has been paid to emissive copper(I) complexes
containing diimine (polypyridine or phenanthroline) ligands in
view of practical applications for chemical sensors, display devices
and solar-energy conversion schemes [1]. Among the studies, the
photophysical properties of the mixed-ligand Cu(I) complexes
involving both diimines and diphosphines are notable, and thus
extensive studies of the complexes have been reported [2–4].
[Cu(dmp)(DPEphos)]+(dmp = 2,9-dimethyl-1,10-phenanthroline;
DPEphos = bis[2-(diphenylphosphino)phenyl]ether) and [Cu(dbp)
(DPEphos)]+(dbp = 2,9-dibutyl-1,10-phenanthroline) exhibit high
quantum yield and a long lifetime in CH2Cl2 at room temperature
[2,3a]. We have been also studying the emissive properties of
mixed-ligand copper(I) complexes with a diimine-type ligand such
as dmp and a diphosphine ligand [4]. However, phosphine deriva-
tives have a disadvantage when they are used in emitting devices.
[5,6]. Reigle et al. reported the luminescence of [Cu(dmp)-
(S@PPh3)2]BF4 and [Cu2(dmp)2(dppbS2)2]BF4(dppbS2 = 1,2-bis-
(diphenylphosphino)butanedisulfide) only at 77 K [7]. However,
most of the studies about Cu(I) complexes with phosphine sulfides
are limited to the structural aspects.
In this study, photophysical properties of the Cu(I) mixed-
ligand complexes containing phosphinesulfides and diimines have
been examined. They are the analogies of our previously reported
mixed-ligand Cu(I) complexes containing phosphines [4].
2. Experimental
2.1. General procedures
All reactions were carried out under argon atmosphere
using Schlenk techniques although the products are air-stable.
2,9-Dimethyl-1,10-phenanthroline (dmp) were purchased from
TCI Co. Ltd. [Cu(CH3CN)]PF6 [8], 2,9-diphenyl-1,10-phenanthroline
(dpp) [9], dppmS2 and dppaS2À [10] were synthesized by the liter-
ature methods. Elemental analyses of the complexes were per-
formed on the Perkin–Elmer model 2400 CHN Analyser. NMR
Since they have soft and strong
r-donor character of trivalent
phosphorus atoms, they are easily oxidized in air or with light in
the presence of air, even though triaryl phosphines are relatively
stable on coordination with metal complexes (see Scheme 1).
Unlike phosphines, phosphine sulfides have pentavalent phos-
phorus atoms, so that they are stable for oxidation. In addition, sul-
fur atoms can function as soft donors, so phosphinesulfide can be
spectra were obtained using a JEOL
chemical shifts are referenced to tetramethylsilane (1H; as inter-
nal) or 85% H3PO4
31P{1H}; as external). Absorption and lumines-
K-400 spectrometer, in which
* Corresponding authors. Tel.: +81 422373759; fax: +81 422373871 (T. Tsukuda);
tel.: +81 422 37 3752; fax: +81 422 37 3871 (T. Tsubomura).
E-mail addresses: tsukuda@st.seikei.ac.jp (T. Tsukuda), tsubomura@st.seikei.
ac.jp (T. Tsubomura).
(
cence spectra were measured with an Agilent 8453 spectrometer
and a Shimadzu RF-5000 fluorometer, respectively.
0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.05.041

A. Dairiki et al. / Polyhedron 28 (2009) 2730–2734
2731
(C25H22P2S2)]PF6: C, 54.13; H, 3.96; N, 3.24. Found: C, 54.26; H,
S
S
N
N
S
S
N
N
Cu
[Cu(CH CN) ]PF
4.14; N, 2.75%. 31P NMR (acetone-d6, 25 °C): d 35.0.
+
+
6
3
4
2.3.2. [Cu(dmp)(dppaS2À)] (2)
dmp (0.11 g, 0.5 mmol) and K(dppaS2À) (0.24 g, 0.5 mmol) were
dissolved in 10 ml of acetone. [Cu(CH3CN)4]PF6 (0.19 g, 0.5 mmol)
was then gradually added to the solution. The solution was stirred
for 2 h at room temperature and an orange powder was obtained.
Recrystallization of the powder from acetone/diethylether gave
orange crystals. Yield 0.31 g (85%). Anal. Calc. for [Cu(C14H12N2)-
(C24H20NP2S2)]: C, 63.36; H, 4.48; N, 5.83. Found: C, 63.18; H,
4.21; N, 5.69%. 31P NMR (acetone-d6, 25 °C): d 31.8.
Scheme 1. Synthesis of mixed-ligand complexes.
Ph Ph
Ph
N
Ph
S P
-
P
S
CH2
P
S
P
S
Ph Ph
Ph Ph
2.3.3. [Cu(dpp)(dppaS2À)] (3)
dppmS2 dppaS2
This complex was prepared by a similar method used for the
preparation of complex 3; use of dpp (0.17 g, 0.5 mmol) instead
of dmp gave purple crystals. Yield 0.29 g (71%). Anal. Calc. for
[Cu(C24H16N2)(C24H20NP2S2)]: C, 68.27; H, 4.30; N, 4.98. Found: C,
67.84; H, 4.09; N, 5.01%. 31P NMR (acetone-d6, 25 °C): d 31.2.
Fig. 1. Phosphinesulfide ligands.
2.2. X-ray measurements
X-ray crystallographic measurements were made on a Rigaku
Saturn 70 CCD area detector with graphite-monochromated Mo
3. Result and discussion
Ka radiation. The crystal-to-detector distance was 54.90 mm. The
3.1. Synthesis and crystal structures
data were collected at a temperature of À150 1 °C to a maximum
2h value of 57.5°. 1800 oscillation images were collected and the
data were processed by using the CrystalClear software [11].
Absorption corrections were made by the numerical method for
complex 1 and 2, and by the spherical method for complex 3.
The intensity of the diffraction for complex 3 was weaker than that
of the others, so complex 3 gave relatively high refinement residu-
als. The structure was solved by direct methods (SIR-92 [12]) and
was refined by full matrix least squares procedures (SHELX-97
[13]). The non-hydrogen atoms are refined anisotropically and
the positions of all hydrogen atoms were fixed at calculated posi-
tions. All calculations were performed by using the CrystalStruc-
ture crystallographic software package [14].
Treatment of [Cu(CH3CN)4]PF6 with equimolar amount of dmp
and dppmS2 in acetone gave the mixed-ligand complex 1. Attempt
to prepare a similar complex to complex 1 by using dppaS2 instead
À
of dppmS2 gave complex 2 containing dppaS2 in which a proton
on an amine moiety is eliminated from dppaS2. Use of KdppaS2
and dmp also led complex 2 readily. Treatment of KdppaS2 and
[Cu(CH3CN)4]+ with dpp instead of dmp gave complex 3.
The single crystals with X-ray quality of 1–3 were obtained by
gradual addition of diethylether into the reaction solution. Struc-
tural data are summarized in Table 1. The structure of complex cat-
ion 1 is shown in Fig. 2. It was found that the complex has the
tetrahedral structure in which each copper center is coordinated
by dmp and dppmS2 chelate ligands. Selected bond lengths, bond
angles and torsion angles of 1 are shown in Table 2. The S–P bond
lengths of 1 in dppmS2 are 1.9670(7) and 1.9784(7) Å. Since it has
been reported that P–S single-bond distance is 2.14 Å and P@S
double-bond distance ranges from 1.916 to 1.959 Å, the P–S bond
length in 1 shows the bonds almost have double-bond character
[15]. The bond angle of S–Cu–S is 108.10(2)°, which is similar to
that in the ideal tetrahedral structure. The chelate ring made of
Cu-dppmS2 moiety is like a twist boat, as deduced from the torsion
angles within the chelate ring ranging from 14.6(2)° to 75.38(12)°.
2.3. Synthesis of mixed-ligand Cu(I) complexes
2.3.1. [Cu(dmp)(dppmS2)]PF6 (1)
dmp (0.11 g, 0.50 mmol) and dppmS2 (0.22 g, 0.50 mmol) were
dissolved in 10 ml of acetone. [Cu(CH3CN)4]PF6 (0.19 g, 0.50 mmol)
was then gradually added to the solution. After the solution was
stirred for 2 h at room temperature, addition of diethylether
(20 ml) to the solution gave orange crystals, which are collected
by filtration. Yield 0.33 g (76%). Anal. Calc. for [Cu(C14H12N2)-
Table 1
Crystallographic data for complex 1, 2 and 3.
Complex name
Complex 1Áacetone
Complex 2 (2 molecules)
Complex 3
Formula
H40CuF6N2P3S2C42
0.25 Â 0.25 Â 0.20
triclinic
O
C76H64Cu2N6P4S4
0.40 Â 0.20 Â 0.10
monoclinic
P21/c (#14)
10.649(6)
19.599(10)
32.222(17)
90
92.990(3)
90
6716.1(60)
4
C48H36CuN3P2S2
0.20 Â 0.16 Â 0.12
monoclinic
P21/c (#14)
10.111(4)
21.340(8)
17.981(7)
90
95.231(2)
90
3863.8(25)
4
Crystal size (mm)
Lattice type
space group
a (Å)
b (Å)
c (Å)
ꢀ
P1 (#2)
10.996(2)
11.249(2)
17.783(3)
98.444(3)
92.604(2)
107.468(3)
2066.1(7)
2
a
(°)
b (°)
(°)
c
3
V (Å
)
Z
Dcalcd (g cmÀ3
)
1.484
8.09
1.425
9.03
1.452
7.97
l
(Mo K
a
) (cmÀ1
)
R1
0.033
0.052
0.079
wR2
0.080
0.099
0.219

2732
A. Dairiki et al. / Polyhedron 28 (2009) 2730–2734
Fig. 2. X-ray structure of complex cation 1.
Fig. 3. X-ray structure of complex of 2. The figure shows one of the two
independent molecules in the unit cell.
Table 2
Selected bond distances (Å), bond angles (°) and torsion angles (°) in complex 1.
Cu(1)–S(1)
Cu(1)–S(2)
Cu(1)–N(1)
Cu(1)–N(2)
S(1)–P(1)
2.2771(6)
2.3333(6)
2.1060(16)
2.0578(18)
1.9784(7)
1.9670(7)
S(2)–P(2)
S(2)–Cu(1)–S(1)
Cu(1)–S(1)–P(1)
Cu(1)–S(2)–P(2)
N(2)–Cu(1)–N(1)
108.10(2)
103.91(3)
100.09(3)
80.91(6)
Cu(1)–S(1)–P(1)–C(39)
Cu(1)–S(2)–P(2)–C(39)
S(1)–Cu(1)–S(2)–P(2)
S(2)–Cu(1)–S(1)–P(1)
S(1)–P(1)–C(39)–P(2)
S(2)–P(2)–C(39)–P(1)
À40.47(8)
À41.55(7)
63.78(2)
À23.74(3)
75.38(12)
À22.75(14)
À
The structures of complex 2 and 3 containing dppaS2 are de-
scribed in Figs. 3 and 4. The selected bond lengths, bond angles
and torsion angles of 2 and 3 are summarized in Tables 3 and 4,
respectively. Complex 2 showed two independent molecules in
the unit cell. The coordination geometry in one of the molecules
is almost similar to each other. There are little differences between
the structures of two independent molecules; the maximum of
deviation for the corresponding bond angles is no more than
Fig. 4. X-ray structure of complex of 3.
repulsion from bulÀky phenyl rings of dpp, which forces the chelate
ring of the dppaS2 to be more planar.
À
3.0°. In the dppaS2 complexes, the S–P bond lengths range from
2.0043(8) to 2.0145(8) Å, which are slightly longer than those of
1. The elongation should reflect the decrease of the P–S bond order,
as shown in other reported transition metal complexes containing
3.2. Spectroscopic properties
NMR spectra have been measured to study the structures of the
mixed-ligand complexes in solution. In the 31P NMR spectra of 1, a
signal assigned as dppmS2 was observed as a distinct singlet at d
35.0, which is slightly shifted compared with the free ligand (d
35.3), and no signals assigned to free ligand were observed. In
addition, the phosphorus signal of 1 was shifted to higher field
than that of [Cu(dppmS2)2]PF6, which shows a singlet signal at d
35.3. It suggests that the complexes keep mixed-ligand coordina-
tion even in solutionÀ. The spectra of 2 and 3 also show only a sin-
glet signal of dppaS2 moiety.
À
dppaS2 ligand [10]. The bond angle of S–Cu–S in 2 is 117.77(2)°
and 119.01(2)°, which iÀs larger than that of 1. It suggests that the
chelate ring of dppaS2 is somewhat more planar than that of
dppmS2. In addition, torsion angles within the chelate in 2
(11.28(4)–44.25(10)°) is smaller than those in 1 and the mean
deviations from the least-squares planes which consists of six
atoms in Cu-dppaS2 chelate ring of two independent complexes
of 2 are 0.238 and 0.256 Å, whereas that of 1 is 0.439 Å. They also
show the planarity of the chelates in 2. It should be caused by the
negative charge on the imino nitrogen of the anionic ligand,
The absorption spectra of 1–3 in acetone are shown in Fig. 5.
The absorption maximum of complex 1 is 457 nm with moderate
dppaS2À, which promotes delocalization of
p-electron within the
S–P–N–P–S chelate. The coordination environment of 3 is similar
to that of 2. However, the torsion angles within the chelate ring
of dppaS2À are much smaller than those in 2, and the mean devia-
tion from the least-squares plane in Cu-dppaS2 chelate ring of 3 is
the smallest of the three complexes (0.120 Å). So they suggest that
3 has a more planar chelate ring of dppaS2À. It may be due to the
intensity. (
e
= 3.1 Â 103 molÀ1 dm3 cmÀ1) It has been reported that
mixed-ligand copper(I) complexes containing phenanthroline
derivatives and diphosphines show absorption maxima ranging
from 400 to 360 nm which have been assigned to MLCT transitions
[2–4]. The band maximum of 1 are shifted to lower energy com-
pared with the [Cu(diimine)(diphosphine)] complexes, but the

A. Dairiki et al. / Polyhedron 28 (2009) 2730–2734
2733
Table 3
Selected bond distances (Å), bond angles (°) and torsion angles (°) in complex 2.
5.0
Cu(1)–S(1)
Cu(1)–S(2)
Cu(1)–N(1)
Cu(1)–N(2)
S(1)–P(1)
2.2761(7)
2.2957(7)
2.126(2)
2.124(2)
2.0130(8)
2.0043(8)
S(2)–P(2)
2.5
S(1)–Cu(1)–S(2)
Cu(1)–S(1)–P(1)
Cu(1)–S(2)–P(2)
N(1)–Cu(1)–N(2)
117.77(2)
100.92(3)
102.06(3)
79.18(8)
ε
Cu(1)–S(1)–P(1)–N(3)
Cu(1)–S(2)–P(2)–N(3)
S(1)–Cu(1)–S(2)–P(2)
S(2)–Cu(1)–S(1)–P(1)
S(1)–P(1)–N(3)–P(2)
S(2)–P(2)–N(3)–P(1)
44.25(10)
40.71(10)
À24.10(4)
À11.28(4)
À40.4(2)
À13.9(2)
0
400
500
600
700
Cu(2)–S(3)–P(3)–N(6)
Cu(2)–S(4)–P(4)–N(6)
S(3)–Cu(2)–S(4)–P(4)
S(4)–Cu(2)–S(3)–P(3)
S(3)–P(3)–N(6)–P(4)
S(4)–P(4)–N(6)–P(3)
Cu(2)–S(3)
Cu(2)–S(4)
Cu(2)–N(4)
Cu(2)–N(5)
S(3)–P(3)
À39.21(10)
À39.51(10)
23.85(4)
9.10(4)
35.2(2)
15.5(2)
2.2768(7)
2.2909(7)
2.128(2)
2.118(2)
2.0145(8)
2.0068(8)
Wavelength / nm
Fig. 5. Absorption spectra of complex cation 1 (solid line), 2 (dotted line) and 3
(dashed line) in acetone at room temperature.
than that of complex 1 which should reflect the stronger ligand
field of dppaS2À. The shoulder band in lower energy region may
be assigned to the second MLCT or LLCT as discussed for complex
1. Complex 3 has an absorption maximum at 578 nm, which is
S(4)–P(4)
shifted to lower energy due to extended
p conjugated system of
S(3)–Cu(2)–S(4)
Cu(2)–S(3)–P(3)
Cu(2)–S(4)–P(4)
N(4)–Cu(2)–N(5)
119.01(2)
101.62(3)
101.26(3)
79.60(8)
dpp compared with dmp. In order to confirm this hypothesis, the
redox processes have been studied by cyclic voltammetry. Unfortu-
nately, the redox potential in the cathodic region is too negative to
estimate the potential for a diimine/diimineÀ redox couple. How-
ever, shoulder cathodic current in complex 3 was observed at
À1.85 V versus SCE, which are clearly less negative than that of
complex 1 and 2. It may suggest that the red shift observed for
dpp complex is reflected in a less negative ligand-based reduction
process.
Table 4
Selected bond distances (Å), bond angles (°) and torsion angles (°) in complex 3.
Cu(1)–S(1)
Cu(1)–S(2)
Cu(1)–N(1)
Cu(1)–N(2)
S(1)–P(1)
2.2470(11)
2.3048(11)
2.106(3)
2.154(3)
2.0065(15)
2.0021(14)
Both 1 and 2 show photoluminescence in the solid state as
shown in Fig. 6. The emission maxima for 1 and 2 are 592 and
661 nm, respectively. The emissive excited states are assigned to
S(2)–P(2)
MLCT transitions involving of the
p* orbital of dmp, as deduced
from the luminescent behavior of [Cu(dmp)2]+ and other mixed-li-
gand complexes. The Stokes shift observed for 2 (240 nm) is con-
siderably large, whereas that of 1 is ca. 140 nm. It has been
shown that a relatively large Stokes shift observed in Cu(I) com-
S(1)–Cu(1)–S(2)
Cu(1)–S(1)–P(1)
Cu(1)–S(2)–P(2)
N(1)–Cu(1)–N(2)
121.14(4)
104.00(5)
104.88(5)
79.57(13)
Cu(1)–S(1)–P(1)–N(3)
Cu(1)–S(2)–P(2)–N(3)
S(2)–Cu(1)–S(1)–P(1)
S(1)–Cu(1)–S(2)–P(2)
S(1)–P(1)–N(3)–P(2)
S(2)–P(2)–N(3)–P(1)
11.25(16)
À0.14(17)
9.91(7)
À14.88(7)
À39.8(4)
32.1(4)
band is reasonably assigned to MLCT involving the
p
* orbitals of
the dmp ligand, because the coordination of the sulfide having
weaker -donor character leads to a decrease of energy levels of
* orbitals interactions in the complex and a decrease of the CT
r
d
r
excitation energy [16]. However, there is another shoulder band
in the lower energy region (500–550 nm) for complex 1. The two
bands may arise from two MLCT transitions to different p* orbitals
of the phen ligand as shown in [Ru(bpy)(CN)4]2À which contains
two quite distinct MLCT absorptions associated with the bpy ligand
[17]. A second possibility is that the second absorption band might
be assigned to a LLCT (ligand-to-ligand charge transfer) from the
electron-rich S-donor ligand to the electron-poor phen ligands.
The absorption maximum of complex 2 is 427 nm. The absorp-
800
700
600
500
Wavelength / nm
*
p
tion band is also assigned to MLCT transition involving the
Fig. 6. Solid-state emission spectra of 1 (solid line) and 2 (dotted line) at room
orbital of dmp, whereas the maximum is shifted to higher energy
temperature.

2734
A. Dairiki et al. / Polyhedron 28 (2009) 2730–2734
plexes results from flattening distortion which occurs in the MLCT
excited state [1a]. It suggests that the extent of distortion on exci-
tation may become larger in 2 than 1, which has relatively higher
planarity of phosphinesulfide chelate than 1 as shown by X-ray
analysis.
For both 1 and 2, no emission is observed in solution. It con-
trasts with the fact that [Cu(dmp)(dppe)]+ and [Cu(dmp)(dppp)]+
emit in solution [2,4b]. It may be caused by the fact that coordina-
tion sphere around the copper atom of the diphosphine sulfide
complexes is less crowded than the diphosphine complexes. The
less crowded structure allows (1) the metal center to facilitate
tetragonal flattening distortion of the excited luminophore and
(2) the solvent molecules to attack the metal center in the excited
states. These quenching mechanism [1a] should effectively affect
the photophysical properties in solution.
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4. Conclusions
Mixed-ligand Cu(I) complexes containing diimine and chelating
phosphinesulfide ligands were synthesized. The isolated com-
plexes, which have pseudo tetrahedral structure, were relatively
stable in air. Two complexes of dmp show emission in the solid
state, and their bands are assigned to MLCT.
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University of Göttingen, Germany, 1997.
5. Supplementary data
[14] CrystalStructure, ver.3.80: Single Crystal Structure Analysis Software,
Molecular Structure Corporation.
[15] T.S. Lobana, Prog. Inorg. Chem. 37 (1989) 495 (and references herein).
[16] S. Sakaki, H. Mizutani, Y. Kase, Inorg. Chem. 31 (1992) 4575.
[17] M. Kovács, A. Horváth, Inorg. Chim. Acta 335 (2002) 69.
CCDC 715718, 715719 and 715720 contain the supplementary
crystallographic data for 1, 2 and 3, respectively. These data can
be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk.