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Crystal structure and the role of cation group factor in the third-order nonlinear optical properties of cadmium complexes constructed by 1 3-dithiole-2-thione-4 5-dithiolato ligand.

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Full Paper
Received: 15 May 2011
Revised: 10 September 2011
Accepted: 22 September 2011
Published online in Wiley Online Library
( DOI 10.1002/aoc.1852
Crystal structure and the role of cation group
factor in the third-order nonlinear optical
properties of cadmium complexes constructed
by 1,3-dithiole-2-thione-4,5-dithiolato ligand
Ting Bin Li, Ya Li Hu, Chun Lin Ma*, Guo Fang He, Ren Gao Zhao and
Guo Bing Zhen
A cadmium complex bis(benzyltriethylammonium) bis(1,3-dithiole-2-thione-4,5-dithiolato)-cadmium(II) ((TEBA)2[Cd(DMIT)2]) has
been synthesized and its crystal structure has been determined by means of X-ray single-crystal diffraction. The central cadmium
(II) ion coordinates with two DMIT, which constructed a distorted tetrahedron environment. Its third-order nonlinear optical properties have been studied using Z-scan technique with 20 ps pulses at wavelength 1064 nm. Its third-order nonlinear susceptibility
x(3) value was determined to be 1.24 1019 m2 V2, the figure of merit, x(3)/a0, was estimated to be 2.64 1020 m3 V2.
Copyright © 2011 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: crystal structure; third-order nonlinear optics; Z-scan
role of charge balance in crystals have a shielding effect on their
third-order nonlinear optical properties for complexes constructed
by DMIT ligands.[11] In this communication the synthesis, singlecrystal structure and third-order nonlinear optical properties of bis
(benzyltriethylammonium) bis(1,3-dithiole-2-thione-4,5-dithiolato)cadmium(II) ((TEBA)2[Cd(DMIT)2]) are studied.
Third-order nonlinear optical materials have attracted much
attention because of their potential utility in ultrafast optical switching and modulation,[1] optical power limiting,[2,3] two-photon
upconversion lasing,[4] 3D optical data storage,[5] and photodynamic
therapy,[6] as well as other fields; also, various types of metal-organic
compounds have been synthesized and studied to obtain materials
with large molecular second hyperpolarizability (g) value.[7,8] It has
been generally accepted that strong nonlinearities in organic
molecules usually arise from highly delocalized p-electron systems.[9] However, there are no theoretical determination or scaling
rules for phonon-mediated multi-photon absorption and, for the
General Methods
All reagents and solvents were commercial grade and purified
prior to use when necessary. The IR spectrum was recorded with
+ CdCl +
r.t. , 4 h
Cd 2S
S + 4Cl
Scheme 1. Synthesis of (TEBA)2[Cd(DMIT)2]
Appl. Organometal. Chem. 2011, 25, 867–870
* Correspondence to: Chun Lin Ma, Department of Material Science and Technology, Taishan University, Taian City, Shandong Province 271021, China.
Department of Material Science and Technology, Taishan University, Taian
City, Shandong Province, 271021, China
Copyright © 2011 John Wiley & Sons, Ltd.
dispersion of the associated nonlinear refraction, no theoretical
determination of the relationship between third-order nonlinear
optical properties and the structure of the complexes.[10] An
important point that should be made has to do with the shielding
effect idea. We have found that the cation groups which play the
T. B. Li et al.
a Nicolet 6700 spectrometer in the region of 400–4000 cm1 using
the KBr pellet technique. The linear absorption spectra in acetone
solution at a concentration of 5.03 105 mol l1 was recorded at
20 C with a Hitachi U-4100 spectrometer. 1H and 13C NMR spectra
were recorded with a Bruker Avance 400 spectrometer, with
acetone-d6 as solvent and tetramethylsilane as internal reference.
Chemical shifts are expressed in d (ppm).
Synthesis and Recrystallization of (TEBA)2[Cd(DMIT)2]
Figure 1. The z-scan experimental apparatus
The synthesis method of DMIT ligand was the same as in
Steimecke et al.[12] Cadmium chloride was used as metal-centre
source for the complex and benzyltriethylammonium chloride
(TEBA) was used as the source of cation groups (Scheme 1). IR
(KBr): ~v = 2842.1, 2922.9, 2966.9, 2994.8 (n[CH]), 1450.0, 1467.9,
1468.2 (n[C-N]), 1406.6 (n[C = C]), 1153.8, 1168.8, 1180.3 (n[C = S]),
1041.1 (n[C-C]), 874.2, 910.2, 985.1 (n[C-S]) 459.3 (n[Cd-S]). 1H
NMR: d = 3.61–3.57 (m, 1H, C5–C9), 3.39 (s, 2H, C12), 2.06–2.04
(m, 2H, C10, C13, C15), 1.95 (s, 3H, C11, C14, C16). 13 C NMR:
d = 207.55, 204.99, 204.79, 204.59 (m, C5–C9), 135.07 (s, C1,
C1A, C2, C2A), 51.88, 51.85, 51.82 (t, C3, C3A), 29.07, (s, C10,
C13, C15), 28.11 (s, C11, C14, C16), 5.53 (s, C12).
Single crystals suitable for X-ray structure determination
were obtained by recrystallization in its acetonitrile solution.
X-ray Crystallographic and Linear Absorption Spectra Study
Figure 2. Motif structure of (TEBA)2[Cd(DMIT)2], with thermal ellipsoids
set at 30% probability
Structure determination was performed on Bruker Smart Apex
II CCD X-ray diffractometer equipped with graphite monochromatic Mo Ka radiation (l = 0.71073 Å) for data collection
by using Φ and o scan mode at 293(2) K. Absorption corrections
Figure 3. Crystal packing, viewed from the b axis
Copyright © 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2011, 25, 867–870
Third-order nonlinear optics
were applied using the SADABS program.[13] The structure was
solved by direct methods and refined by full-matrix leastsquares calculations for 207 parameters. All the calculations
were carried out with SHELXL-97 program[14] with anisotropic
thermal parameters for the non-hydrogen atoms. All hydrogen
atoms were placed in the calculated positions and refined
isotropically using a riding model. The final R = 0.0593,
wR = 0.0765 ðo ¼ 1=½s2 ðF0 2 Þ þ ð0:0010PÞ2 þ 0:2000P; where P ¼
ðF0 2 þ 2Fc 2 Þ=3Þ , (Δ/s)max = 0.000, S = 0.916, (Δr)max = 0.480 and
(Δr)min = 0.395 e 3.
Third-order Nonlinear Optical Properties Measurements
The third-order nonlinear optical properties measurements were
performed using single-beam Z-scan technique[15] as shown in
Fig. 1. Its operation involves measurements of the far-field sample
transmittance (transmitted energy detected by D2 divided by input
energy monitored by D1) of a focused Gaussian beam as a function
of the sample position (z) relative to the beam waist. The light
source is a mode-locked Nd:YAG laser (Continuum Leopard D-10,
20 ps, 10 Hz, 1064 nm), the focal length of the positive lens is
f = 25 cm and the transmitted energy was measured with Molectron
J3S-10 energy sensor in combination with EPM2000 2-Channel laser
power and energy meter (Coherent Corp.) in the far field. To eliminate the thermal effect induced by non-radiative relaxation effects
on our measurements results, we performed the Z-scan under different pulse energies (3.46, 5.31 and 5.85 mJ) to ensure that the phase
shift had a linear relation with on-axis irradiance at focus. To guarantee that the nonlinear optical phenomenon we observed was not
derived from solvent, we performed a Z-scan on the solvent at the
highest pulse energy in our experiments and no obvious nonlinear
optical phenomenon was observed. The concentration of the titled
complex’s acetone solution was 9.56 103 mol l1.
Figure 4. The linear absorption spectra of (Me4N)2[Cd(DMIT)2] and
Results and Discussion
Crystal Structure and Linear Absorption Spectra of (TEBA)2
Appl. Organometal. Chem. 2011, 25, 867–870
Figure 5. The normalized closed aperture Z-scan of (TEBA)2[Cd(DMIT)2]
solution in acetone (9.56 103 mol l1), placed in a 1 mm path-length
quartz cell, using 20 ps pulses as a function of irradiance at l = 1064 nm:
(a) experimental results; (b) theoretical fitted results
Third-Order Nonlinear Optical Properties Study
Figure 5(a) shows the normalized transmittance for closeaperture Z-scan measurement results, and the theoretical fitted
results are shown in Figure 5(b). For the closed-aperture Z-scan
measurement results, the normalized transmittance T relates
position z through the following equation:[18]
T ðx; Δf0 Þ ¼ 1 þ
Copyright © 2011 John Wiley & Sons, Ltd.
ðx 2
ð3 x 2 Þ
Δf 2
þ 9Þðx þ 1Þ
ðx þ 9Þðx 2 þ 1Þ
The motif structure of the crystal is shown in Fig. 2. Crystal data
for this complex are as follows: monoclinic, space group C2/c,
a = 31.106(6), b = 8.3138(16), c = 19.699(4) Å, b = 128.698(13) ,
V = 3975.9(14) Å3, Z = 4, F(000) = 1832. Cadmium(II) ion is coordinated with four sulphur atoms of two DMIT, which constructed a
distorted tetrahedron. The Cd1-S4 and Cd1-S5 bond lengths
are 2.507(2) Å and 2.5162(18) Å. The S4-Cd1-S4A, S4-Cd1-S5,
S4-Cd1-S5A and S5-Cd1-S5A bond angles are 112.87(11) , 89.64
(6) , 128.72(7) and 111.90(9) , respectively, which are in the
common range.[16] Figure 3 shows the crystal packing diagram
that from the b axis. We employed the PLATON program[17] to
calculate the hydrogen bonds and found that there is only one
kind of hydrogen bond: C9–H5S2 (3.789(12) Å) in the crystals.
The cation groups and complexes are linked to each other through
this hydrogen bond contacts. Figure 4 shows the linear absorption spectra of (Me4N)2[Cd(DMIT)2] and (TEBA)2[Cd(DMIT)2]. The
intense absorption band of (TEBA)2[Cd(DMIT)2] located around
580 nm is the metal-ligand charge transfer (MLCT) absorption.
This MLCT band is red-shifted about 100 nm in comparison with
that of (Me4N)2[Cd(DMIT)2]. This change is attributable to the
presence of larger cation groups in (TEBA)2[Cd(DMIT)2] than in
T. B. Li et al.
Table 1. Third-order nonlinear optical properties of (TEBA)2[Cd(DMIT)2]
m W )
m /V )
mW )
m V )
where x = z/z0, z0 = po02/l is the Rayleigh range of the beam;
Δf ¼ knI2 I0 Leff is phase-shift derived from nonlinear refraction;
Δc ¼ bI0 Leff =2 2 is phase-shift derived from nonlinear absorption; K = 2p/l is a wave vector. I0 is peak intensity, which relates the
pulse energy x through the equation I0 ¼ 4 ln2x=p =2 o2 t.[19]
Leff ¼ ð1 ea0 L Þ=a0 is effect sample length. The imaginary part
of the third-order nonlinear susceptibility w(3) is related to b
ð3 Þ
through wI ¼ e0 n20 cl=3p b (SI) and the real part of w(3) is related
to nI2 through wR
12 2
m2 V2)
(1056 C m4 V3)
(1053 m4 s)
the third-order nonlinear optical properties of these kinds of
Supplemental data CCDC-719701 contains the supplementary crystallographic data for this communication. These data
can be obtained free of charge at
where e0 = 8.85 10
c Nm
is the electric permittivity of free space, n0 is the linear refractive
index, c is the speed light in free space and l is the wavelength.
Supporting information may be found in the online version of
this article.
Thus w(3) can be determined through the equation wð3Þ ¼
2nI2 n20 e0 c (SI),
(m V ). The g is related to w
through the
equation g(m C V ) = (e0/f N) w (m C V ) and f ¼ n20 þ 2 =3
is the local field factor. All results are listed in Table 1. From
the table we know that the g value of (TEBA)2[Cd(DMIT)2] is
7.32 1056 C m4 V3, which is about five times smaller than
that of (Me4N)2[Cd(DMIT)2].[20] This difference can only be attributed to the cation groups, i.e. TEBA+ of (TEBA)2[Cd(DMIT)2] are
larger than the cation groups, i.e. Me4N+ of (Me4N)2[Cd(DMIT)2],
so its shielding effect on the third-order nonlinear optical properties is stronger than that of (Me4N)2[Cd(DMIT)2].
A cadmium complex has been synthesized and its structure has
been determined by means of X-ray single-crystal diffraction. Its
third-order nonlinear optical properties have been studied using
Z-scan technique. The figure of merit, w(3)/a0, was estimated to be
2.64 1020 m3 V2. As the results show, it possesses fine thirdorder nonlinear optical properties in comparison with other
previously reported complexes. For example, Benjamin J. Coe
et al. have reported g values of Ru(II) and Fe(II) complexes
with pyridinium substituent ligands in the range (13–
5500) 1036 esu;[21] J. Tedim et al. have reported nI2 values of
nickel(II) and copper(II) complexes with salen ligands in the
range (8.52–26.7) 1021 m2 W1;[22] and K. Kandasamy et al.
have reported that g values of most phthalocynines are of the
order of 1032 esu.[23] Thus it possesses promising applications
in the fields of ultrafast optical switching and modulation, optical limiting, fluorescence excitation microscopy and imaging,
three-dimensional optical data storage, etc. By comparing its g
value with that of the same complex but possessing different
cation groups, we certificated that cation groups playing the
role of charge balance in crystals have a shielding effect on
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Appl. Organometal. Chem. 2011, 25, 867–870
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crystals, constructed, nonlinear, properties, optical, group, cadmium, thione, complexes, cation, third, ligand, order, factors, structure, dithiolato, dithiol, role
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