www.elsevier.

nl/locate/poly

Polyhedron 19 (2000) 1545 1549

Synthesis, crystal structure and third-order optical nonlinearity of

a flywheel-shaped cluster, [MoS4Cu3(dppm)3][BF4]2H2O
Weilian Tan a, Hegen Zheng b, Qionghua Jin c, Guocheng Jin b, Wei Ji a,
Deliang Long d, Xinquan Xin b,*
a
Department of Physics, National Uni6ersity of Singapore, Singapore 119260, Singapore
b
State Key Laboratory of Coordination Chemistry Institute, Nanjing Uni6ersity, Nanjing 210093, PR China
c
Department of Chemistry, Capital Normal Uni6ersity, Beijing 100037, PR China
d
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, PR China
Received 16 November 1999; accepted 10 April 2000

Abstract

The title compound [MoS4Cu3(dppm)3][BF4]]2H2O (dppm =Ph2PCH2PPh2) was synthesized for nonlinear optical studies by
the reaction of (Et4N)2MoS4 and [Cu2(dppm)2(MeCN)4][BF4]2 in CH3CN solution. Single-crystal X-ray analysis revealed that
three copper atoms and the MoS42 form a distorted flywheel array with WCu separations of 2.7754(14), 2.792(2) and 2.820
(2) A, . The third-order nonlinear optical properties were investigated by a Z-scan technique with 7 ns laser pulses at 532 nm. It
was observed that the nonlinear absorption is very small, but it has considerable third-order large nonlinear refractive index.
2000 Elsevier Science Ltd. All rights reserved.

Keywords: Tetrathiometalate; Nonlinear optical properties; Synthesis; Copper compounds; Crystal structures; Dppm

The tetrathiometallates MS42 (M =Mo, W) have
been shown to be able to act as multidentate ligands
with a variety of transition metal ions [1]. They have
been used extensively as starting materials in synthesiz-
ing Mo(W) containing inorganic clusters [2,3] and in
catalytic studies [4,5]. Studies on these clusters have
been expanded to include their third-order nonlinear
optical (NLO) properties in our laboratory. Tradition-
ally, NLO research has been largely focused on conju-
gated polymers, semiconductors and discrete organic
molecules [6,7]. In our search for better NLO materials
we have undertaken a series of studies on the structure
and NLO properties of Mo(W)Cu(Ag, Au, Pd)S
clusters [814]. In this article, we report the synthesis,
X-ray crystal structure and nonlinear optical properties
of a novel cluster compound containing m4-S:
[MoS4Cu3(dppm)3][BF4]2H2O. We also compare its
* Corresponding author. Tel.: +86-25-359-3132; fax: + 86-25-331-
4502.
E-mail address: xxin@netra.nju.edu.cn (X. Xin).
third-order NLO absorptive and refractive properties
with those of other reported cluster compounds.
1. Experimental
1.1. Reagents
The reaction was performed under anaerobic condi-
tions using standard Schlenk techniques; solvents were
purified, distilled and degassed prior to use. The
reagents [Et4N]2[MoS4] and [Cu2(dppm)2(MeCN)4]-
[BF4]2 were prepared according to the literature [15,16].
1.2. Physical measurements
Infrared spectra were recorded on a Fourier Nicolet
FT-170SX spectrophotometer with pressed KBr pellets
and the electronic spectrum of the title cluster was
measured with a Hitachi U-3410 spectrophotometer.
Carbon and hydrogen analyses were performed on a PE
240C Elemental Analyser.

0277-5387/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 0 ) 0 0 3 9 9 - 5
1546 W. Tan et al. / Polyhedron 19 (2000) 15451549

1.3. Nonlinear optical (NLO) measurements solution was comprised somewhat by disorder in the
BF4 ion and solvent water molecules. Rotational dis-
The dimethylforminade (DMF) solution of the title order about the BF1 bond of the BF4 ion was
cluster was contained in a 1-mm thick quartz cuvette modeled with another three F atoms each occupying
with concentration of 3.6 10 4 M. The sample was two half-weighted sites. All BF distances were re-
irradiated by a Q-switched frequency-doubled Nd:YAG strained to be similar with a standard deviation of 0.03
laser, which produced linearly polarized 7 ns (FWHM) A, using SADI instruction (SHELXTL Version 5) [18], as
optical pulses at 532 nm. The laser was operated at a were all FF distances within each idealized tetrahe-
pulse repetition rate of 10 Hz. The spatial profiles of dron. The four solvent water oxygen atoms contained a
the optical pulses were nearly Gaussian after passing site-occupancy factor of 0.5. All non-hydrogen atoms in
through a spatial filter. The laser beam was then di- the cation portion were refined anisotropically. Hydro-
vided by a beam splitter into two parts: one was used as gen atoms riding on carbon atoms (CH = 0.95 A, ) were
a reference for the incident energy and the other was introduced in ideal positions and refined with an
focused onto the sample by a focusing mirror of 25 cm isotropic temperature factor 20% greater than that of
focal length. The minimum beam radius of the focused the parent atoms. No attempts were made to generate
laser beam was determined to be 309 5 mm. Both hydrogen atoms for solvent water molecules. Refine-
incident and transmitted pulse energies were measured ment of the structure was carried out by full-matrix
simultaneously by two energy detectors (Rjp-735 energy least-squares methods, and the final cycle of full-matrix
probes, Laser Precision), which were linked to a com- least-squares refinement converged to give R=0.0678
puter by an IEEE interface. The NLO properties of the and wR= 0.1661. The crystallographic data and details
sample were determined by performing the Z-scan mea- concerning the intensity are summarized in Table 1.
surements [17]. The sample was mounted on a transla-
tion stage that was controlled by a computer to move
along the Z-axis with respect to the focal point. To 2. Results and discussion
determine both the sign and magnitude of the nonlinear
refraction, a 1.0 mm diameter aperture was placed in 2.1. Structure of the title compound
front of the transmission detector and the transmittance
was recorded as a function of the sample position on The ORTEP diagram of the cation [MoS4Cu3-
the Z-axis (closed-aperture Z-scan). For measuring the (dppm)3]+ of the title compound is depicted in Fig. 1.
nonlinear absorption, the Z-dependent sample transmit- The selected bond lengths and angles are given in
tance was taken without the aperture (open-aperture Tables 2 and 3. The Mo atom has retained its initial
Z-scan). tetrahedral coordination, with SMoS angles in the
range of 107.06(11)112.79(12). The three Cu
1.4. Syntheses
Table 1
1.4.1. [MoS4Cu3(dppm)3][BF4] 2H2O Crystal data and data collection parameters
A mixture of [Cu2(dppm)2(MeCN)4][BF4]2 (237.3 mg,
Formula C75H70O2MoCu3S4P6BF4
0.1923 mmol) and (Et4N)2MoS4 (93 mg, 0.1923 mmol)
in acetonitrile (25 ml) was stirred at room temperature Formula weight 1686.71
for 2 h. The volume of the solution was reduced to 5 ml Crystal system monoclinic
and an orange precipitate was obtained upon the addi- Space group P2(1)
tion of diethyl ether. Vapor diffusion of diethyl ether a (A, ) 13.0481(2)
b (A, ) 16.9413(2)
into a CH2Cl2 solution gave a product isolated as an c (A, ) 17.8930(1)
air-stable orange crystalline solid. Anal. Calc. for b () 93.255(1)
C75H70BCu3F4MoO2P6S4: C, 53.28; H, 4.17; Found: C, V (A, 3) 3948.9(8)
53.60; H, 4.20%. IR spectra (KBr pellet): MoS, 480.0 Z 2
and 454.8 cm 1. Crystal size (mm) 0.450.250.10
T (K) 296
Dcalc (g cm3) 1.419
1.5. X-ray structure determination F(000) 1712
m (cm1) 1.231
An orange crystal with dimension of 0.45 0.25 Reflections measured 15976
0.10 mm was stuck to the end of a glass fiber by using Unique reflections 9800
Observation 7895 (I\2.0s(I))
neutral jelly, which was mounted on a Siemens
Parameters refined 851
SMART CCD area-detecting diffractometer. The struc- Goodness-of-fit 1.067
ture was solved by using a direct method and expanded Largest shift 0.000
with subsequent Fourier syntheses. The quality of the
 W. Tan et al. / Polyhedron 19 (2000) 15451549 1547

Table 3
Selected angles () for the title compound

S1MoS2 110.37(13) S1MoS3 111.77(13)

S2MoS3 112.79(12) S1MoS4 107.06(11)
S2MoS4 107.41(10) S3MoS4 107.11(11)
S1MoCu2 126.07(10) S2MoCu2 54.31(9)
S3MoCu2 121.84(10) S4MoCu2 53.24(6)
S1MoCu3 125.62(9) S2MoCu3 123.60(11)
S3MoCu3 54.18(9) S4MoCu3 52.97(7)
Cu2MoCu3 84.96(4) P32Cu1P11 132.86(12)
P32Cu1S4 105.46(12) P11Cu1S4 108.75(11)
P32Cu1S1 99.24(12) P11Cu1S1 105.07(13)
S4Cu1S1 100.75(1) P21Cu2P12 120.56(11)
P21Cu2S4 106.12(11) P12Cu2S4 101.75(10)
P21Cu2S2 114.49(12) P12Cu2S2 109.07(12)
S4Cu2S2 102.30(10) P22Cu3P31 124.21(12)
P22Cu3S4 104.94(10) P31Cu3S4 100.72(10)
P22Cu3S3 116.78(12) P31Cu3S3 104.62(11)
S4Cu3S3 102.17(11)

to the rigidity of the [MoS4]2 group and the steric

Fig. 1. The ORTEP diagram of the cation [MoS4Cu3(dppm)3]+ of the
title compound.
atoms and the MoS42 form a distorted flywheel
array. There are two different coordination modes of
the bridging S atom. The atoms S1, S2 and S3 are
bonded to Mo and only one Cu atom, but S4 adopts a
m4-bridging mode, being bonded to Mo and the three
Cu atoms. Each of the three Cu atoms is in a distorted
tetrahedron. Compounds with a m4-S moiety asymmet-
rically bonded to two kinds of metal ion are not
unprecedented in the literature. Examples include (n-
Bu4N)2[MoOS3Cu3(NCS)3], [MoCu2OS3(PPh3)3] and
[NEt4]3[WOS3(CuBr)3(m-Br)]2H2O [19 21]. The
MoCu bond lengths [2.7754(14), 2.792(2) and 2.820(2)
A, ] are longer than those observed in
[Et4N]4[Mo2O2S6Cu6I6] (av. 2.661 A, ) [22], but compara-
ble with those of (n-Bu4N)2[MoOS3Cu3(NCS)3]. Each
of the three copper atoms is in a distorted tetrahedron.
The six-membered ring comprising Cu, S, Cu, P, C and
P has a boat conformation, whereas the other related
rings have a chair conformation. This is probably due
crowding of the phenyl groups of dppm.
2.2. The third-order NLO properties of the title
compound
The electronic spectrum of the title compound in
DMF is depicted in Fig. 2. It was noted that the
compound has relatively low linear absorption in the
visible and near-IR region. The lowest absorption peak
is located at 560 nm. The Z-scan results for the com-
pound are shown in Fig. 3, where the filled circles were
the Z-scan data measured without the aperture and the
open circles were the results obtained from the division
of the closed aperture Z-scan data by the open aperture
Z-scan data. To obtain the NLO parameters we em-
ployed a Z-scan theory [17], which considers nonlinear-
ities of third-order nature. The total absorption
coefficient can be written as a=a0 + a2I, where a0 and

Table 2
Selected bond lengths (A, ) for the title compound

MoS1 2.191(3) MoS2 2.192(3)

MoS3 2.205(3) MoS4 2.286(3)
MoCu1 2.820(2) MoCu2 2.7754(14)
MoCu3 2.792(2) Cu1S1 2.358(4)
Cu1S4 2.317(3) Cu2S2 2.326(3)
Cu2S4 2.310(2) Cu3S3 2.335(3)
Cu3S4 2.309(3) Cu1P11 2.302(3)
Cu1P32 2.300(3) Cu2P21 2.294(3)
Cu2P12 2.300(3) Cu3P22 2.293(3)
Cu3P31 2.309(3) Fig. 2. Electronic spectrum of [MoS4Cu3(dppm)3][BF4]2H2O (3.6
10-4 M) ( ) DMF. The optical path is 1 mm.
1548 W. Tan et al. / Polyhedron 19 (2000) 15451549

g=
1 ') ) ) )
9 108o0n 20c 2a2 2 cn 20n2 2
+ (1)
NF 4 4pv 80p 2
where o0 and c are the permittivity and the speed of
light in a vacuum, respectively, v is the angular fre-
quency of the light, N the concentration of the cluster
(in cm3) and F 4 = 3 is the local Lorentz field factor. We
Fig. 3. The normalised Z-scan data [MoS4Cu3(dppm)3][BF4]2H2O
(3.6 10 4 M) in DMF solution with 532 nm, 7 ns laser pulses. The
optical path is 1 mm. The peak incident irradiance of the pulses at
focus is 420 MW cm 2. The experimental data were measured
without ( ) an aperture. The open circles () were obtained by
dividing the Z-scan data collected with the aperture by those collected
without the aperture, they have been vertically displaced by 0.4 for
clarity. The solid curves are the theoretical fits based on the Z-scan
theory.
a2 are the linear and nonlinear absorption coefficients,
respectively, and I is the irradiance of the laser beam
within the sample. The total refractive coefficient can
be expressed as n = n0 +n2I, where n0 and n2 are the
linear and nonlinear refractive indices. The good fits
between the theory and our experimental data suggest
that the observed NLO phenomena can be expressed
effectively by third-order susceptibilities. In Fig. 3, it
was observed that the compound shows a negative sign
for n2. This indicates that the laser beam propagating in
it undergoes a self-defocusing process. Table 4 lists the
measured nonlinear absorption coefficient, a2, and non-
linear refractive index, n2, for the title compound. In
accordance with the observed a2 and n2 values, the
modulus of the third-order molecular susceptibility g
can be calculated using Eq. (1)
calculated that g= 2.4 10 29 esu for the title com-
pound. This calculated value is several orders of magni-
tude greater than the well known NLO materials (for
example 1 10 32 1 10 31 esu for metallophthalo-
cyanines at 1064 nm [23] and 7.5 10 34 esu for C60 at
1910 nm [24]). It should be noted that the Z-scan
measurements reported here could not reveal the origin
of the measured a2 and n2 values for the title com-
pound. Excited-state effects, two-photon absorption,
third-order bound-electronic effect and nonlinear scat-
tering are the possible mechanism behind the observed
nonlinearities [2527]. The observed self-defocusing
property possessed by the compound shows that it can
be a promising material for applications such as protec-
tion of optical sensors. It is also interesting to compare
this compound with other different structural clusters
such as twin-nested, nested and butterfly-shaped clus-
ters [9,19,20,22]. Table 4 shows that the title compound
is comparable with most of the other clusters in terms
of the effective n2 value.
3. Supplementary data
Supplementary data are available from the Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge, CB2 1EZ, UK on request, quoting the
deposition number 135206.
Acknowledgements
This research was supported by the National Natural
Science Foundation of China and the National Univer-
sity of Singapore.

Table 4
The NLO parameters for cluster compounds a

Compound Structure ao (cm1 M1) a2 (cm W1 M1) n2 (cm2 W1 M1)

[MoS4Cu3(dppm)3][BF4]]2H2O b flywheel 5.50103 1.1105 5.51010

(n-Bu4N)2[MoOS3Cu3(NCS)3] [19] nested 0.40103 1.8106 3.81010
[MoOS3Cu3I(py)5] [9] nested 0.04103 2.5105 1.31010
[WOS3Cu3I(py)5] [9] nested 2.10103 15.0105 16.01010
[Et4N][Mo2O2S6Cu6I6] [22] twin-nested 0.74103 2.0105 3.01010
[WOS3Cu2(PPh3)3] [20] butterfly 2.50103 6.71010

a
Note: ao is the linear absorption coefficient; a2 is the nonlinear absorption coefficient; n2 is the nonlinear refractive index. The dashed line
represents negligible nonlinear absorption coefficient.
b
This Work.
 W. Tan et al. / Polyhedron 19 (2000) 15451549
References
[1] A. Muller, E. Diemann, R. Jostes, H. Bogge, Angew. Chem., Int.
Ed. Engl. 20 (1981) 934.
[2] J.P. Lang, X.Q. Xin, J. Solid State Chem. 108 (1994) 118.
[3] J.G. Li, X.Q. Xin, Z.Y. Zhou, K.B. Yu, J. Chem. Soc., Chem.
Commun. (1991) 250.
[4] R.H. Holm, Chem. Soc. Rev. 10 (1981) 455.
[5] L. Bremner, C.F. Mills, B.W. Young, J. Inorg. Biochem. 16
(1982) 109.
[6] D.S. Chenla, J. Zyss (Eds.), Nonlinear Optical Properties of
Organic Molecules and Crystals, Academic Press, Orlando, FL,
1987.
[7] H. Haug (Ed.), Optical Nonlinearities and Instabilities in Semi-
conductors, Academic Press, Boston, MA, 1988.
[8] H.G. Zheng, W. Ji, M.K.M. Low, G. Sakane, T. Shibahara,
X.Q. Xin, J. Chem. Soc., Dalton Trans. (1997) 2537.
[9] P. Ge, S.H. Tang, W. Ji, S. Shi, H.W. Hou, D.L. Long, X.Q.
Xin, S.F. Lu, Q.J. Wu, J. Phys. Chem. B. 101 (1997) 27.
[10] S. Shi, W. Ji, S.H. Tang, J.P. Lang, X.Q. Xin, J. Am. Chem.
Soc. 116 (1994) 3615.
[11] W. Ji, S. Shi, H.J. Du, P. Ge, S.W. Tang, X.Q. Xin, J. Phys.
Chem. 99 (1995) 17297.
[12] M.K.M. Low, H.W. Hou, H.G. Zheng, W.T. Wong, G.X. Jin,
X.Q. Xin, W. Ji, Chem. Commun. 4 (1998) 505.
[13] D.X. Zeng, W. Ji, W.T. Wong, W.Y. Wong, X.Q. Xin, Inorg.
Chim. Acta 279 (1998) 172.
.
.
1549
[14] H.W. Hou, H.G. Zheng, H.G. Ang, Y.T. Fan, M.K.M. Low, Y.
Zhu, W.L. Wang, X.Q. Xin, W. Ji, W.T. Wong, J. Chem. Soc.,
Dalton Trans. (1999) 2953.
[15] J.W. McDonald, G.D. Friesen, L.D. Rosenhein, W.E. Newton,
Inorg. Chem. Acta 72 (1983) 205.
[16] J. Diez, M.M.P. Gamcia, J. Gimeno, A. Tiripicchio, M.T.
Camellini, J. Chem. Soc., Dalton Trans. (1987) 1275.
[17] M. Sheik-Bahae, A.A. Said, T.H. Wei, D.J. Hagan, E.W. Van
Stryland, IEEE J. Quant. Electron. 26 (1990) 760.
[18] Siemens (1994), SHELXTL, Version 5 Reference Manual, Siemens
Energy & Automation Inc., Madison, WI, USA.
[19] S. Shi, W. Ji, W. Xie, T.C. Chong, H.C. Zeng, J.P. Lang, X.Q.
Xin, Mater. Chem. Phys. 39 (1995) 298.
[20] H.W. Hou, X.Q. Xin, J. Liu, M.Q. Chen, S. Shi, J. Chem. Soc.,
Dalton Trans. (1994) 3211.
[21] S. Shi, H.W. Hou, X.Q. Xin, J. Phys. Chem. 99 (1995) 4050.
[22] H.W. Hou, D.L. Long, X.Q. Xin, X.Y. Huang, B.S. Kang, P.
Ge, W. Ji, S. Shi, Inorg. Chem. 35 (1996) 5363.
[23] J.S. Shirk, J.R. Lindle, F.J. Bartoli, Z.H. Kafafi, A.W. Snow, in:
S.R. Marder, J.E. Sohn, G.D. Stucky (Eds.), Materials for
Nonlinear Optics, American Chemical Society, Washington,
1992, p. 626.
[24] Y. Wang, L.T. Cheng, J. Phys. Chem. 96 (1992) 1530.
[25] W. Ji, W. Xie, S.H. Tang, S. Shi, Mater. Chem. Phys. 43 (1995)
1.
[26] M. Sheik-Bahae, D.C. Hutching, D.J. Hagan, E.W. Van Stry-
land, Phys. Rev. Lett. 65 (1991) 96.
[27] K. Mansour, M.J. Soileau, E.W. Van Stryland, J. Opt. Soc. Am.
B 9 (1992) 1100.