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Cu cluster: Cation-directed synthesis, crystal structure and nonlinear optical property
Accepted Manuscript A Supra-Cubane-Like Mo/S/Cu Cluster: Cation-Directed Synthesis, Crystal Structure and Nonlinear Optical Property Jinfang Zhang, Weitao Chen, Yu Fang, Ding Jia, Yinlin Wang, Yinglin Song, Chi Zhang PII: DOI: Reference:
S0277-5387(15)00399-X http://dx.doi.org/10.1016/j.poly.2015.07.044 POLY 11430
To appear in:
Polyhedron
Received Date: Accepted Date:
4 June 2015 15 July 2015
Please cite this article as: J. Zhang, W. Chen, Y. Fang, D. Jia, Y. Wang, Y. Song, C. Zhang, A Supra-Cubane-Like Mo/S/Cu Cluster: Cation-Directed Synthesis, Crystal Structure and Nonlinear Optical Property, Polyhedron (2015), doi: http://dx.doi.org/10.1016/j.poly.2015.07.044
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A Supra-Cubane-Like Mo/S/Cu Cluster: Cation-Directed Synthesis, Crystal Structure and Nonlinear Optical Property Jinfang Zhang a,*, Weitao Chen b, Yu Fang c, Ding Jia b, Yinlin Wang b, Yinglin Song c, Chi Zhang a,* a
China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, P.R. China b
China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 212013, P. R. China c
School of Physical Science and Technology, Soochow University, Suzhou 215006, P.R. China
………………………………………………………………………………………… Abstract: Directed by potassium-crownether host-guest cation, a unique octameric eicosanuclear
heterothiometallic
Mo/S/Cu
cluster
[K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] (1) was synthesized by the reaction of (NH4)2MoS4, CuI, KI, dibenzo-18-crown-6 in DMF solution. 1 was characterized by elemental analysis, IR, thermogravimetric analysis, X-ray powder and single crystal diffractions. 1 crystallizes in the tetragonal space group I41cd. The anionic octameric eicosanuclear [Mo8S32Cu12]4- cluster exhibits a supra-cubane-like skeleton, fabricated by four nest-shaped clusters [Mo(µ 1-S)(µ 3-S)3Cu3]+ and four flywheel-shaped clusters [Mo(µ 2-S)3(µ 4-S)Cu3]+ linking together through shared Cu atoms. The cation [K(dibenzo-18-crown-6)(DMF)2]+ of 1 exhibits the host-guest configuration, where K+ is embedded in the center of dibenzo-18-crown-6. Furthermore, Z-scan studies (532 nm, 21 ps pulses) reveal that 1 possesses effective third-order nonlinear optical (NLO) properties. Keywords
Heterothiometallic
Mo/S/Cu
cluster;
Supra-cubane-like
skeleton;
Nonlinear optical property ………………………………………………………………………………………… *Corresponding authors: [email protected]
Introduction Heterothiometallic clusters have attracted much attention not only for their rich cluster skeletons [1], but also for potential applications in material science [2-4]. In recent years, Mo(W)/S/Cu(Ag) cluster polymers or cluster-organic frameworks have been extensively explored due to their fascinating architectures, topologies [5-7] as well as promising applications in solvatochromism [8], adsorption [9] and nonlinear optical (NLO) materials [10-11], etc. However, the Mo(W)/S/Cu(Ag) cluster oligomers have attracted reducing attention in the past decade. In fact, the Mo(W)/S/Cu(Ag) cluster oligomers still have varieties of architectures and applications [1, 12-15]. For example, the cluster {[WS4Cu4Br2(phen)2]2·MeCN} exhibits a rare dimeric architecture and strong photocatalytic activity [12]; [(n-Bu)4N]4[Mo4Cu 10S16O3]·H2O obtains the tetrameric tetradecanuclear cluster architecture [13]; the tetrameric cluster [Et4N]4[Mo4Cu 8O4S12{(Ph2PS)2N}4] exhibits the novel dodecanuclear cluster structure and effective NLO properties [14]; and two isomorphous tetrameric clusters [Sr(DMAC)6]2[M4S16Ag4] (M = Mo, W) show the unusual octanuclear planar “open” square-like skeletons and distinct NLO refraction behaviors [15]. However, the effective methods for Mo(W)/S/Cu(Ag) cluster oligomers are very scarce [13-17], which heavily hinders the formation of various Mo(W)/S/Cu(Ag) cluster oligomers. Therefore, developing effective preparative approaches is very important for Mo(W)/S/Cu(Ag) cluster oligomers. Herein, an effective host-guest cation-directed synthesis has been developed to construct the Mo(W)/S/Cu(Ag) cluster oligomers. Structural studies reveal a unique anionic eicosanuclear
supra-cubane-like
Mo/S/Cu
octameric
cluster
for
[K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] (1). Furthermore, third-order NLO properties of this unique Mo/S/Cu cluster have been investigated. Experimental Section All reactions and manipulations were carried out in an open reactor at ambient temperature. The solvents DMF, i-PrOH and the chemicals dibenzo-18-crown-6, KI
and CuI were obtained commercially without further purification. (NH4)2MoS4 was prepared according to the literature method [18]. Elemental analysis for C, H and N was performed on a FLASH 1112A micro-analyzer. The infrared spectrum (4000-400 cm-1) was recorded from KBr discs with Nicolet Nexus 470 transform spectrometer. TGA was performed using a TGA/STA 449C instrument (heating rate of 5 /min, nitrogen stream). Powder X-ray diffraction (PXRD) pattern was recorded using Cu Kα1 radiation on a Shimadzu XRD-6000 diffractometer. Synthesis of [K(dibenzo-18-crown-6)(DMF)2]4[Mo 8S32Cu 12] 1 The solution of dibenzo-18-crown-6 (0.1440 g, 0.4 mmol) and KI (0.0996 g, 0.6 mmol) in 2 ml DMF was added into a black-red solution of (NH4)2MoS4 (0.1040 g, 0.4 mmol) and CuI (0.1140 g, 0.6 mmol) in 2 ml DMF. The mixed solution was stirred for about 10 min at room temperature, and then filtrated. The filtrate was layered with 6 ml i-PrOH on the surface. Several days later, 1 was obtained as black-red block crystals (yield: 0.0735 g, 31 % based on Mo). Anal. Calc. for C104H152Cu12K4Mo8N8O32S32: C, 26.36 %; H, 3.24 %; N, 2.36 %; Found: C, 26.25 %; H, 3.19 % N, 2.40 %. IR (KBr pellet, cm-1): 1672 (vs), 1249 (s), 1124 (s), 482 (s), 462 (s), 444 (s). Crystal structure determination The crystal of 1 suitable for single-crystal X-ray analysis was obtained directly from the above preparation. All measurements were made on a Rigaku Saturn724+ CCD X-ray diffractometer by using monochromated Mo Kα (λ = 0.71073 Å). Single crystal of 1 was mounted with grease at the top of a thin glass fiber. Cell parameter was refined on all observed reflections by using the program Crystalclear (Rigaku Inc., 2007). The collected data were reduced by the program CrystalClear and an absorption correction (multiscan) was applied. The reflection data for 1 were also corrected for Lorentz and polarization effects. The crystal structure of 1 was solved by direct methods and refined on F2 by full-matrix least-squares methods using the SHELXTL-97
software
package
[19].
In
each
cation
[K(dibenzo-18-crown-6)(DMF)2]+, one of the two DMF ligands is heavily distorted. Only parts of atoms from distorted DMF ligands (O8 and C24 in K1 cation; O16, N3, C56 and C58 in K2 cation) can be found. The existence of these distorted DMF ligands can be confirmed by the elemental analysis and TGA. The highest peak (0.836 e Å-3) and deepest hole (-0.617 e Å-3) are around O8 and Mo4 atoms, respectively. A summary of the key crystallographic information is listed in Table 1. The important bond lengths and angles for 1 are listed in Tables 2 and 3, respectively. More detailed crystallographic data have been given in its CIF file. CCDC: 1403705 Nonlinear Optical Measurements The NLO properties were determined by performing Z-scan measurements [20]. Aniline solution sample was placed in a 2 mm quartz cuvette for the NLO measurements, which were performed with linearly polarized 21 ps pulses with different energies at 532 nm generated from a Q-switched frequency-doubled Nd:YAG laser. 1 is stable toward air and laser light under the experimental conditions. The spatial profiles of the optical pulses were of nearly Gaussian transverse mode. The pulsed laser was focused onto the sample cell with a 40 cm focal length mirror. The spot radius of the laser beam was measured to be 24 µm. The energy of the input and output pulses were measured simultaneously by precision laser detectors (Rjp-735 energy probes), which were linked to a computer by an IEEE interface [21], while the incident pulse energy was varied by a Newport Com. Attenuator. The interval between the laser pulses was chosen to be 10 Hz to avoid the influence of thermal and other longer-term effects. The sample was mounted on a translation stage that was controlled by computer to move along the axis of the incident laser beam (Z-direction) with respect to the focal point. To determine both the sign and magnitude of the nonlinear refraction, a 5 mm diameter aperture was placed in front of the transmission detector and the transmittance recorded as a function of the sample position on the Z-axis (closed-aperture Z-scan). To measure the nonlinear absorption, the Z-dependent sample transmittance was taken without the aperture (open-aperture Z-scan).
Results and Discussion Synthetic method Some effective methods (e.g. cation-directed synthesis, solvothermal synthesis, preformed cluster synthesis etc) had been successfully developed to construct Mo(W)/S/Cu(Ag) cluster polymers or cluster-organic frameworks [22-26]. However, the synthetic methods for the Mo(W)/S/Cu(Ag) cluster oligomers are very rare thus far. Most reported Mo(W)/S/Cu(Ag) cluster oligomers were obtained in the presence of different quaternary ammonium cations or solvent-coordinated metallic cations [13-17]. Herein, the host-gust cation [K(dibenzo-18-crown-6)(DMF)2]+ was selected as the template to direct the assembly of [MoS4]2- moieties and Cu atoms. Compared with the quaternary ammonium and solvent-coordinated metallic cations, host-gust cation [K(dibenzo-18-crown-6)(DMF)2]+ exhibits distinct shape and dimension, and results in a unique anionic supra-cubane-like eicosanuclear Mo/S/Cu cluster. Therefore, this host-gust cation should play the important role in constructing unusual Mo(W)/S/Cu(Ag) cluster oligomers. Crystal structure of [K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] 1 Structural analysis reveals that 1 crystallizes in the tetragonal space group I4 1cd, and contains
the
potassium-crownether
[K(dibenzo-18-crown-6)(DMF)2]+
and
unique
host-guest octameric
cation eicosanuclear
supra-cubane-like anionic Mo/S/Cu cluster [Mo8S32Cu12]4- (Figs. 1-3). There are one half supra-cubane-like anionic Mo/S/Cu cluster and two host-guest cations in the asymmetric unit of 1. The anionic octameric eicosanuclear supra-cubane-like skeleton can be regarded as four nest-shaped clusters [Mo(µ 1-S)(µ 3-S)3Cu3]+ and four flywheel-shaped clusters [Mo(µ 4-S)(µ 2-S)3Cu 3]+ linking together through the shared Cu atoms (Figs. 1-2). This contrasts to the reported supramolecular cube [(Cp*WS3Cu3)8Cl8(CN)12Li4], which is only fabricated by nest-shaped clusters [27]. In the eicosanuclear supra-cubane-like architecture, eight Mo atoms occupy the corners of the cubane, and all adopt the tetrahedral coordination geometry through
bonding to four sulfur atoms (Fig. 1). Mo2 or Mo4 atom is bonded by three µ2-S and one µ4-S atoms; the S-Mo-S angles range from 108.72(9)° to 111.05(8)°. Whereas Mo1 or Mo3 is connected by one µ1-S and three µ3-S atoms; the S-Mo-S angles range from 107.81(18)° to 111.71(10)°. A remarkable feature of this unique cluster is that there are four kinds of S atoms in its skeleton, namely, terminal S, µ2-S, µ3-S and µ4-S in a molar ratio of 1:3:3:1. This has not been found in heterothiometallic Mo(W)/S/Cu(Ag) clusters with different architectures [1, 2, 5]. The average bond lengths of Mo-µ1-S, Mo-µ2-S, Mo-µ3-S and Mo-µ4-S are 2.116 Å, 2.188 Å, 2.247 Å and 2.292 Å, respectively. All Cu atoms in [Mo8S32Cu12]4- cluster are located on the edges of the cubane, and exhibit the same coordination environment. Each Cu atom links with one µ2-S, two µ3-S and one µ4-S atoms to form a tetrahedral coordination geometry. The average bond lengths of Cu-µ2-S, Cu-µ3-S and Cu-µ4-S are 2.310 Å, 2.309 Å and 2.342 Å, separately. In the anionic metallic skeleton of 1 (Fig. 2), the distances between the neighbour Mo and Cu atom range from 2.7083(12) Å to 2.7532(13) Å, which are obviously shorter than the van der Waals contact distance of 4.06 Å for Mo···Cu. [28] Therefore, there is obvious interaction between neighbour Mo and Cu atoms. In the asymmetric unit, two host-guest cations have the same coordination environment, thus only K1 cation is described here in detail (Fig. 3). It is very interesting that the cation exhibits a “satellite-receiver”-shaped configuration (Fig. 3). K1 atom is eight-coordinated by two O atoms from DMF and six O atoms from dibenzo-18-crown-6 (Fig. 3a), and
locates nearly at the
center
of the
dibenzo-18-crown-6 plane (the plane of dibenzo-18-crown-6 is defined by its six O atoms), where the K1-O distances range from 2.7067(4) to 2.8072(4) Å. Two DMF molecules bond with K1 atom via their respective O atoms, and locate on two sides of dibenzo-18-crown-6 plane. TGA and PXRD for 1 The thermal stability of 1 was investigated (Fig. 4). The first weight loss of 11.87 % in the region 140-250 °C corresponds to the loss of DMF molecules (calcd: 12.34 %)
(Fig. 4). The second rapid weight loss of 24.35 % in the region 250-450 °C is in accordance with the loss of dibenzo-18-crown-6 molecules (calcd: 30.42 %). With the increase of the temperature from 450 °C, a gradual weight loss of 4.68 % was found, which should be corresponding to the remaining portion of dibenzo-18-crown-6. As shown in Fig. 5, the peak positions of the experimental and simulated PXRD patterns are in good agreement with each other, which indicates that the crystal structure of 1 is truly representative of the bulk crystal product. NLO properties The third-order NLO properties of 1 were investigated with linearly polarized 21 ps pulses at 532 nm generated from a Q-switched frequency-doubled Nd:YAG laser in 4.1 × 10-5 mol dm-3 aniline solution. Typical result from Z-scan experiment [20] for 1 is displayed in Fig. 6. The nonlinear absorption property of 1 was evaluated under the open-aperture configuration. Fig. 6 displays the nonlinear absorptive behavior and clearly illustrates that the absorption increases with increasing intensity of the incident laser, and the light transmittance (T) drops to 82%. A reasonably good fit between the experimental data and the theoretical curve was achieved, which suggests that the experimentally observed NLO effects have an effective third-order characteristic. The nonlinear absorptive coefficient a2 was calculated to be 5.9 × 10 -12 m W-1 for 1. On the
basis
of
the
NLO
absorptive
value,
the
concentration-independent
hyperpolarizabilities γ, which reflect the integrated third-order NLO properties, was deduced to be 1.5 × 10 -30 esu for 1. The γ value of 1 is comparable to and even larger than those of many other heterothiometallic Mo/S/Cu(Ag) clusters with different skeletons (for representative examples, see Table 4) [14-15, 29-32], which indicates that 1 will be a promising candidate for NLO materials. Conclusions An effective host-guest cation-directed synthesis has been developed to construct a unique anionic supra-cubane-like eicosanuclear Mo/S/Cu cluster. Z-scan studies exhibit that this octameric Mo/S/Cu cluster possesses effective third-order NLO
properties. Further studies of the generation of new heterothiometallic cluster oligomers induced by other host-guest cations and their NLO properties are currently in progress. Appendix A. Supplementary data CCDC (1403705) contains the supplementary crystallographic data for 1. The data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Acknowledgments This research was financially supported by the National Natural Science Foundation of China (50925207, 51172100), the Ministry of Science and Technology of China (2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (IRT1064), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (B13025), Jiangsu Innovation Research Team, Natural Science Foundation of Jiangsu Provence (BK20140163) and the Fundamental Research Funds for the Central Universities (JUSRP1022).
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Fig. 1. The ORTEP diagram of anionic supra-cubane-like eicosanuclear cluster configuration of 1 with 30% probability displacement ellipsoids. (Mo green, Cu red, S yellow; symmetry code: a -x, -y, z)
Fig. 2. The ball and stick diagram of anionic metallic skeleton of 1 (Mo green, Cu red).
Fig.
3.
The
ball
and
stick
diagrams
of
host-guest
cation
[K(dibenzo-18-crown-6)(DMF)2]+ of 1 (the disorder DMF ligands only retain the O atoms; K teal, O pink, N blue, C grey).
Fig. 4. TGA curve for 1.
Fig. 5. Comparison of the PXRD patterns of 1 (the black and red lines represent the simulated and experimental PXRD patterns, respectively; the high-angle part of PXRD patterns was enlarged and inserted).
Fig. 6. Normalized open-aperture Z-scan curves showing NLO absorption of 1 at 532 nm with 21 ps pulse duration (the black squares represent the Z-scan experimental data, and the red solid curve is theoretical fit based on Z-scan theory).
Table 1. Crystal data and structure refinement for 1. 1 Formula
C104H152Cu12K4 Mo8N8O32S32
FW Temperature (K)
4739.10 150(2)
Wavelength (Å)
0.71073
Crystal system
tetragonal
Space group
I4(1)cd
a (Å)
27.766(4)
b (Å)
27.766(4)
c (Å)
42.695(8)
3
V (Å )
32916(9)
Z
8
Dc (Mg m-3)
1.913
-1
µ(mm )
2.670
F(000)
18875
Reflections collected
40919
Unique reflection
13364
Rint
0.0413
GOF on F2
1.062
R1 [I>2σ(I)]
0.0501
wR2 [I>2σ(I)]
0.1087
∆ρmax / ∆ρmin (e Å-3)
0.836 / -0.617
Table 2. Selected bond lengths (Å) for 1. Mo(1)-S(1)
2.109(3)
Mo(1)-S(3)
2.239(2)
Mo(1)-S(16)
2.248(2)
Mo(1)-S(2)
2.248(2)
Mo(2)-S(7)
2.170(3)
Mo(2)-S(4)
2.187(3)
Mo(2)-S(6)
2.196(2)
Mo(2)-S(5)
2.293(2)
Mo(3)-S(10)
2.123(3)
Mo(3)-S(8)
2.242(2)
Mo(3)-S(9)
2.244(2)
Mo(3)-S(11)
2.260(2)
Mo(4)-S(15)
2.182(2)
Mo(4)-S(14)
2.195(2)
Mo(4)-S(13)
2.198(2)
Mo(4)-S(12)
2.291(2)
Cu(1)-S(4)
2.292(3)
Cu(1)-S(3)
2.304(2)
Cu(1)-S(2)
2.308(2)
Cu(1)-S(5)
2.337(3)
Cu(2)-S(8)
2.304(3)
Cu(2)-S(5)
2.307(2)
Cu(2)-S(7)
2.327(3)
Cu(2)-S(9)
2.328(2)
Cu(3)-S(11)#1
2.276(2)
Cu(3)-S(6)
2.302(3)
Cu(3)-S(8)#1
2.331(3)
Cu(3)-S(5)
2.352(2)
Cu(4)-S(11)
2.304(2)
Cu(4)-S(13)
2.306(2)
Cu(4)-S(9)
2.319(3)
Cu(4)-S(12)
2.343(2)
Cu(5)-S(3)
2.296(2)
Cu(5)-S(14)#1
2.308(2)
Cu(5)-S(16)
2.326(2)
Cu(5)-S(12)#1
2.347(2)
Cu(6)-S(16)
2.300(2)
Cu(6)-S(12)
2.305(2)
Cu(6)-S(2)
2.310(2)
Cu(6)-S(15)
2.323(2)
Symmetry transformations used to generate equivalent atoms: #1 -x, -y, z
Table 3. Selected bond angles (º) for 1. S(1)-Mo(1)-S(3)
110.91(9)
S(1)-Mo(1)-S(16)
110.91(10)
S(3)-Mo(1)-S(16)
107.81(8)
S(1)-Mo(1)-S(2)
110.02(10)
S(3)-Mo(1)-S(2)
108.17(9)
S(16)-Mo(1)-S(2)
108.94(8)
S(7)-Mo(2)-S(4)
110.46(12)
S(7)-Mo(2)-S(6)
110.00(11)
S(4)-Mo(2)-S(6)
108.95(11)
S(7)-Mo(2)-S(5)
108.72(9)
S(4)-Mo(2)-S(5)
108.98(10)
S(6)-Mo(2)-S(5)
109.72(9)
S(10)-Mo(3)-S(8)
108.25(11)
S(10)-Mo(3)-S(9)
111.57(11)
S(8)-Mo(3)-S(9)
109.08(9)
S(10)-Mo(3)-S(11)
111.71(10)
S(8)-Mo(3)-S(11)
108.21(9)
S(9)-Mo(3)-S(11)
107.94(9)
S(15)-Mo(4)-S(14)
109.65(9)
S(15)-Mo(4)-S(13)
108.92(8)
S(14)-Mo(4)-S(13)
111.05(8)
S(15)-Mo(4)-S(12)
109.35(8)
S(14)-Mo(4)-S(12)
108.86(8)
S(13)-Mo(4)-S(12)
108.98(9)
S(4)-Cu(1)-S(3)
107.49(10)
S(4)-Cu(1)-S(2)
114.12(9)
S(3)-Cu(1)-S(2)
103.98(9)
S(4)-Cu(1)-S(5)
103.96(10)
S(3)-Cu(1)-S(5)
113.63(9)
S(2)-Cu(1)-S(5)
113.77(8)
S(8)-Cu(2)-S(5)
118.93(9)
S(8)-Cu(2)-S(7)
108.09(11)
S(5)-Cu(2)-S(7)
103.03(9)
S(8)-Cu(2)-S(9)
104.11(9)
S(5)-Cu(2)-S(9)
113.39(10)
S(7)-Cu(2)-S(9)
109.01(10)
S(11)#1-Cu(3)-S(6)
107.57(9)
S(11)#1-Cu(3)-S(8)#1
104.64(9)
S(6)-Cu(3)-S(8)#1
116.16(11)
S(11)#1-Cu(3)-S(5)
119.26(9)
S(6)-Cu(3)-S(5)
104.11(9)
S(8)#1-Cu(3)-S(5)
105.69(9)
S(11)-Cu(4)-S(13)
107.24(8)
S(11)-Cu(4)-S(9)
103.95(10)
S(13)-Cu(4)-S(9)
117.00(8)
S(11)-Cu(4)-S(12)
116.33(8)
S(13)-Cu(4)-S(12)
103.63(9)
S(9)-Cu(4)-S(12)
109.20(8)
S(3)-Cu(5)-S(14)#1
108.83(8)
S(3)-Cu(5)-S(16)
103.31(8)
S(14)#1-Cu(5)-S(16)
114.61(9)
S(3)-Cu(5)-S(12)#1
118.53(9)
S(14)#1-Cu(5)-S(12)#1
103.23(8)
S(16)-Cu(5)-S(12)#1
108.80(8)
S(16)-Cu(6)-S(12)
115.26(8)
S(16)-Cu(6)-S(2)
105.05(8)
S(12)-Cu(6)-S(2)
115.41(10)
S(16)-Cu(6)-S(15)
108.20(9)
S(12)-Cu(6)-S(15)
104.14(8)
S(2)-Cu(6)-S(15)
108.52(8)
Symmetry transformations used to generate equivalent atoms: #1 -x, -y, z
Table 4. The hyperpolarizability values (γ) of some representative heterothiometallic clusters measured at 532 nm. Compound
Structure type
γ (esu)
Ref.
1
supra-cubane-like
1.5×10-30
this work
[Et4N]4[Mo4O4S12Cu8{(Ph2PS)2 N}4]
dodecanuclear square
1.81×10-30
14
{[Sr(DMAC)6 ]2[Mo4 S16Ag4]}
octanuclear square-like
2.13×10-30
15
[Et4N]2[MoS4Cu4(SCN)4(2-pic)4]
planar open shape
1.29×10-31
29
[MoS4Cu4Br2(py)6 ]
planar open shape
1.17 × 10-30
30
[MoOS3Cu3(4-pic)6]· BF4
nest-shape
2.89×10-31
31
[Et4 N]3[MoOS3(µ3-I)(AgI)3]
cubane-like
9.07×10-31
32
A unique anionic octameric supra-cubane-like heterothiometallic Mo/S/Cu cluster was synthesized in the presence of potassium-crownether host-guest cation. Furthermore, Z-scan studies reveal that this cluster possesses effective third-order nonlinear optical properties.
S0277-5387(15)00399-X http://dx.doi.org/10.1016/j.poly.2015.07.044 POLY 11430
To appear in:
Polyhedron
Received Date: Accepted Date:
4 June 2015 15 July 2015
Please cite this article as: J. Zhang, W. Chen, Y. Fang, D. Jia, Y. Wang, Y. Song, C. Zhang, A Supra-Cubane-Like Mo/S/Cu Cluster: Cation-Directed Synthesis, Crystal Structure and Nonlinear Optical Property, Polyhedron (2015), doi: http://dx.doi.org/10.1016/j.poly.2015.07.044
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A Supra-Cubane-Like Mo/S/Cu Cluster: Cation-Directed Synthesis, Crystal Structure and Nonlinear Optical Property Jinfang Zhang a,*, Weitao Chen b, Yu Fang c, Ding Jia b, Yinlin Wang b, Yinglin Song c, Chi Zhang a,* a
China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, P.R. China b
China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 212013, P. R. China c
School of Physical Science and Technology, Soochow University, Suzhou 215006, P.R. China
………………………………………………………………………………………… Abstract: Directed by potassium-crownether host-guest cation, a unique octameric eicosanuclear
heterothiometallic
Mo/S/Cu
cluster
[K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] (1) was synthesized by the reaction of (NH4)2MoS4, CuI, KI, dibenzo-18-crown-6 in DMF solution. 1 was characterized by elemental analysis, IR, thermogravimetric analysis, X-ray powder and single crystal diffractions. 1 crystallizes in the tetragonal space group I41cd. The anionic octameric eicosanuclear [Mo8S32Cu12]4- cluster exhibits a supra-cubane-like skeleton, fabricated by four nest-shaped clusters [Mo(µ 1-S)(µ 3-S)3Cu3]+ and four flywheel-shaped clusters [Mo(µ 2-S)3(µ 4-S)Cu3]+ linking together through shared Cu atoms. The cation [K(dibenzo-18-crown-6)(DMF)2]+ of 1 exhibits the host-guest configuration, where K+ is embedded in the center of dibenzo-18-crown-6. Furthermore, Z-scan studies (532 nm, 21 ps pulses) reveal that 1 possesses effective third-order nonlinear optical (NLO) properties. Keywords
Heterothiometallic
Mo/S/Cu
cluster;
Supra-cubane-like
skeleton;
Nonlinear optical property ………………………………………………………………………………………… *Corresponding authors: [email protected]
Introduction Heterothiometallic clusters have attracted much attention not only for their rich cluster skeletons [1], but also for potential applications in material science [2-4]. In recent years, Mo(W)/S/Cu(Ag) cluster polymers or cluster-organic frameworks have been extensively explored due to their fascinating architectures, topologies [5-7] as well as promising applications in solvatochromism [8], adsorption [9] and nonlinear optical (NLO) materials [10-11], etc. However, the Mo(W)/S/Cu(Ag) cluster oligomers have attracted reducing attention in the past decade. In fact, the Mo(W)/S/Cu(Ag) cluster oligomers still have varieties of architectures and applications [1, 12-15]. For example, the cluster {[WS4Cu4Br2(phen)2]2·MeCN} exhibits a rare dimeric architecture and strong photocatalytic activity [12]; [(n-Bu)4N]4[Mo4Cu 10S16O3]·H2O obtains the tetrameric tetradecanuclear cluster architecture [13]; the tetrameric cluster [Et4N]4[Mo4Cu 8O4S12{(Ph2PS)2N}4] exhibits the novel dodecanuclear cluster structure and effective NLO properties [14]; and two isomorphous tetrameric clusters [Sr(DMAC)6]2[M4S16Ag4] (M = Mo, W) show the unusual octanuclear planar “open” square-like skeletons and distinct NLO refraction behaviors [15]. However, the effective methods for Mo(W)/S/Cu(Ag) cluster oligomers are very scarce [13-17], which heavily hinders the formation of various Mo(W)/S/Cu(Ag) cluster oligomers. Therefore, developing effective preparative approaches is very important for Mo(W)/S/Cu(Ag) cluster oligomers. Herein, an effective host-guest cation-directed synthesis has been developed to construct the Mo(W)/S/Cu(Ag) cluster oligomers. Structural studies reveal a unique anionic eicosanuclear
supra-cubane-like
Mo/S/Cu
octameric
cluster
for
[K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] (1). Furthermore, third-order NLO properties of this unique Mo/S/Cu cluster have been investigated. Experimental Section All reactions and manipulations were carried out in an open reactor at ambient temperature. The solvents DMF, i-PrOH and the chemicals dibenzo-18-crown-6, KI
and CuI were obtained commercially without further purification. (NH4)2MoS4 was prepared according to the literature method [18]. Elemental analysis for C, H and N was performed on a FLASH 1112A micro-analyzer. The infrared spectrum (4000-400 cm-1) was recorded from KBr discs with Nicolet Nexus 470 transform spectrometer. TGA was performed using a TGA/STA 449C instrument (heating rate of 5 /min, nitrogen stream). Powder X-ray diffraction (PXRD) pattern was recorded using Cu Kα1 radiation on a Shimadzu XRD-6000 diffractometer. Synthesis of [K(dibenzo-18-crown-6)(DMF)2]4[Mo 8S32Cu 12] 1 The solution of dibenzo-18-crown-6 (0.1440 g, 0.4 mmol) and KI (0.0996 g, 0.6 mmol) in 2 ml DMF was added into a black-red solution of (NH4)2MoS4 (0.1040 g, 0.4 mmol) and CuI (0.1140 g, 0.6 mmol) in 2 ml DMF. The mixed solution was stirred for about 10 min at room temperature, and then filtrated. The filtrate was layered with 6 ml i-PrOH on the surface. Several days later, 1 was obtained as black-red block crystals (yield: 0.0735 g, 31 % based on Mo). Anal. Calc. for C104H152Cu12K4Mo8N8O32S32: C, 26.36 %; H, 3.24 %; N, 2.36 %; Found: C, 26.25 %; H, 3.19 % N, 2.40 %. IR (KBr pellet, cm-1): 1672 (vs), 1249 (s), 1124 (s), 482 (s), 462 (s), 444 (s). Crystal structure determination The crystal of 1 suitable for single-crystal X-ray analysis was obtained directly from the above preparation. All measurements were made on a Rigaku Saturn724+ CCD X-ray diffractometer by using monochromated Mo Kα (λ = 0.71073 Å). Single crystal of 1 was mounted with grease at the top of a thin glass fiber. Cell parameter was refined on all observed reflections by using the program Crystalclear (Rigaku Inc., 2007). The collected data were reduced by the program CrystalClear and an absorption correction (multiscan) was applied. The reflection data for 1 were also corrected for Lorentz and polarization effects. The crystal structure of 1 was solved by direct methods and refined on F2 by full-matrix least-squares methods using the SHELXTL-97
software
package
[19].
In
each
cation
[K(dibenzo-18-crown-6)(DMF)2]+, one of the two DMF ligands is heavily distorted. Only parts of atoms from distorted DMF ligands (O8 and C24 in K1 cation; O16, N3, C56 and C58 in K2 cation) can be found. The existence of these distorted DMF ligands can be confirmed by the elemental analysis and TGA. The highest peak (0.836 e Å-3) and deepest hole (-0.617 e Å-3) are around O8 and Mo4 atoms, respectively. A summary of the key crystallographic information is listed in Table 1. The important bond lengths and angles for 1 are listed in Tables 2 and 3, respectively. More detailed crystallographic data have been given in its CIF file. CCDC: 1403705 Nonlinear Optical Measurements The NLO properties were determined by performing Z-scan measurements [20]. Aniline solution sample was placed in a 2 mm quartz cuvette for the NLO measurements, which were performed with linearly polarized 21 ps pulses with different energies at 532 nm generated from a Q-switched frequency-doubled Nd:YAG laser. 1 is stable toward air and laser light under the experimental conditions. The spatial profiles of the optical pulses were of nearly Gaussian transverse mode. The pulsed laser was focused onto the sample cell with a 40 cm focal length mirror. The spot radius of the laser beam was measured to be 24 µm. The energy of the input and output pulses were measured simultaneously by precision laser detectors (Rjp-735 energy probes), which were linked to a computer by an IEEE interface [21], while the incident pulse energy was varied by a Newport Com. Attenuator. The interval between the laser pulses was chosen to be 10 Hz to avoid the influence of thermal and other longer-term effects. The sample was mounted on a translation stage that was controlled by computer to move along the axis of the incident laser beam (Z-direction) with respect to the focal point. To determine both the sign and magnitude of the nonlinear refraction, a 5 mm diameter aperture was placed in front of the transmission detector and the transmittance recorded as a function of the sample position on the Z-axis (closed-aperture Z-scan). To measure the nonlinear absorption, the Z-dependent sample transmittance was taken without the aperture (open-aperture Z-scan).
Results and Discussion Synthetic method Some effective methods (e.g. cation-directed synthesis, solvothermal synthesis, preformed cluster synthesis etc) had been successfully developed to construct Mo(W)/S/Cu(Ag) cluster polymers or cluster-organic frameworks [22-26]. However, the synthetic methods for the Mo(W)/S/Cu(Ag) cluster oligomers are very rare thus far. Most reported Mo(W)/S/Cu(Ag) cluster oligomers were obtained in the presence of different quaternary ammonium cations or solvent-coordinated metallic cations [13-17]. Herein, the host-gust cation [K(dibenzo-18-crown-6)(DMF)2]+ was selected as the template to direct the assembly of [MoS4]2- moieties and Cu atoms. Compared with the quaternary ammonium and solvent-coordinated metallic cations, host-gust cation [K(dibenzo-18-crown-6)(DMF)2]+ exhibits distinct shape and dimension, and results in a unique anionic supra-cubane-like eicosanuclear Mo/S/Cu cluster. Therefore, this host-gust cation should play the important role in constructing unusual Mo(W)/S/Cu(Ag) cluster oligomers. Crystal structure of [K(dibenzo-18-crown-6)(DMF)2]4[Mo8S32Cu12] 1 Structural analysis reveals that 1 crystallizes in the tetragonal space group I4 1cd, and contains
the
potassium-crownether
[K(dibenzo-18-crown-6)(DMF)2]+
and
unique
host-guest octameric
cation eicosanuclear
supra-cubane-like anionic Mo/S/Cu cluster [Mo8S32Cu12]4- (Figs. 1-3). There are one half supra-cubane-like anionic Mo/S/Cu cluster and two host-guest cations in the asymmetric unit of 1. The anionic octameric eicosanuclear supra-cubane-like skeleton can be regarded as four nest-shaped clusters [Mo(µ 1-S)(µ 3-S)3Cu3]+ and four flywheel-shaped clusters [Mo(µ 4-S)(µ 2-S)3Cu 3]+ linking together through the shared Cu atoms (Figs. 1-2). This contrasts to the reported supramolecular cube [(Cp*WS3Cu3)8Cl8(CN)12Li4], which is only fabricated by nest-shaped clusters [27]. In the eicosanuclear supra-cubane-like architecture, eight Mo atoms occupy the corners of the cubane, and all adopt the tetrahedral coordination geometry through
bonding to four sulfur atoms (Fig. 1). Mo2 or Mo4 atom is bonded by three µ2-S and one µ4-S atoms; the S-Mo-S angles range from 108.72(9)° to 111.05(8)°. Whereas Mo1 or Mo3 is connected by one µ1-S and three µ3-S atoms; the S-Mo-S angles range from 107.81(18)° to 111.71(10)°. A remarkable feature of this unique cluster is that there are four kinds of S atoms in its skeleton, namely, terminal S, µ2-S, µ3-S and µ4-S in a molar ratio of 1:3:3:1. This has not been found in heterothiometallic Mo(W)/S/Cu(Ag) clusters with different architectures [1, 2, 5]. The average bond lengths of Mo-µ1-S, Mo-µ2-S, Mo-µ3-S and Mo-µ4-S are 2.116 Å, 2.188 Å, 2.247 Å and 2.292 Å, respectively. All Cu atoms in [Mo8S32Cu12]4- cluster are located on the edges of the cubane, and exhibit the same coordination environment. Each Cu atom links with one µ2-S, two µ3-S and one µ4-S atoms to form a tetrahedral coordination geometry. The average bond lengths of Cu-µ2-S, Cu-µ3-S and Cu-µ4-S are 2.310 Å, 2.309 Å and 2.342 Å, separately. In the anionic metallic skeleton of 1 (Fig. 2), the distances between the neighbour Mo and Cu atom range from 2.7083(12) Å to 2.7532(13) Å, which are obviously shorter than the van der Waals contact distance of 4.06 Å for Mo···Cu. [28] Therefore, there is obvious interaction between neighbour Mo and Cu atoms. In the asymmetric unit, two host-guest cations have the same coordination environment, thus only K1 cation is described here in detail (Fig. 3). It is very interesting that the cation exhibits a “satellite-receiver”-shaped configuration (Fig. 3). K1 atom is eight-coordinated by two O atoms from DMF and six O atoms from dibenzo-18-crown-6 (Fig. 3a), and
locates nearly at the
center
of the
dibenzo-18-crown-6 plane (the plane of dibenzo-18-crown-6 is defined by its six O atoms), where the K1-O distances range from 2.7067(4) to 2.8072(4) Å. Two DMF molecules bond with K1 atom via their respective O atoms, and locate on two sides of dibenzo-18-crown-6 plane. TGA and PXRD for 1 The thermal stability of 1 was investigated (Fig. 4). The first weight loss of 11.87 % in the region 140-250 °C corresponds to the loss of DMF molecules (calcd: 12.34 %)
(Fig. 4). The second rapid weight loss of 24.35 % in the region 250-450 °C is in accordance with the loss of dibenzo-18-crown-6 molecules (calcd: 30.42 %). With the increase of the temperature from 450 °C, a gradual weight loss of 4.68 % was found, which should be corresponding to the remaining portion of dibenzo-18-crown-6. As shown in Fig. 5, the peak positions of the experimental and simulated PXRD patterns are in good agreement with each other, which indicates that the crystal structure of 1 is truly representative of the bulk crystal product. NLO properties The third-order NLO properties of 1 were investigated with linearly polarized 21 ps pulses at 532 nm generated from a Q-switched frequency-doubled Nd:YAG laser in 4.1 × 10-5 mol dm-3 aniline solution. Typical result from Z-scan experiment [20] for 1 is displayed in Fig. 6. The nonlinear absorption property of 1 was evaluated under the open-aperture configuration. Fig. 6 displays the nonlinear absorptive behavior and clearly illustrates that the absorption increases with increasing intensity of the incident laser, and the light transmittance (T) drops to 82%. A reasonably good fit between the experimental data and the theoretical curve was achieved, which suggests that the experimentally observed NLO effects have an effective third-order characteristic. The nonlinear absorptive coefficient a2 was calculated to be 5.9 × 10 -12 m W-1 for 1. On the
basis
of
the
NLO
absorptive
value,
the
concentration-independent
hyperpolarizabilities γ, which reflect the integrated third-order NLO properties, was deduced to be 1.5 × 10 -30 esu for 1. The γ value of 1 is comparable to and even larger than those of many other heterothiometallic Mo/S/Cu(Ag) clusters with different skeletons (for representative examples, see Table 4) [14-15, 29-32], which indicates that 1 will be a promising candidate for NLO materials. Conclusions An effective host-guest cation-directed synthesis has been developed to construct a unique anionic supra-cubane-like eicosanuclear Mo/S/Cu cluster. Z-scan studies exhibit that this octameric Mo/S/Cu cluster possesses effective third-order NLO
properties. Further studies of the generation of new heterothiometallic cluster oligomers induced by other host-guest cations and their NLO properties are currently in progress. Appendix A. Supplementary data CCDC (1403705) contains the supplementary crystallographic data for 1. The data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Acknowledgments This research was financially supported by the National Natural Science Foundation of China (50925207, 51172100), the Ministry of Science and Technology of China (2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (IRT1064), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (B13025), Jiangsu Innovation Research Team, Natural Science Foundation of Jiangsu Provence (BK20140163) and the Fundamental Research Funds for the Central Universities (JUSRP1022).
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Fig. 1. The ORTEP diagram of anionic supra-cubane-like eicosanuclear cluster configuration of 1 with 30% probability displacement ellipsoids. (Mo green, Cu red, S yellow; symmetry code: a -x, -y, z)
Fig. 2. The ball and stick diagram of anionic metallic skeleton of 1 (Mo green, Cu red).
Fig.
3.
The
ball
and
stick
diagrams
of
host-guest
cation
[K(dibenzo-18-crown-6)(DMF)2]+ of 1 (the disorder DMF ligands only retain the O atoms; K teal, O pink, N blue, C grey).
Fig. 4. TGA curve for 1.
Fig. 5. Comparison of the PXRD patterns of 1 (the black and red lines represent the simulated and experimental PXRD patterns, respectively; the high-angle part of PXRD patterns was enlarged and inserted).
Fig. 6. Normalized open-aperture Z-scan curves showing NLO absorption of 1 at 532 nm with 21 ps pulse duration (the black squares represent the Z-scan experimental data, and the red solid curve is theoretical fit based on Z-scan theory).
Table 1. Crystal data and structure refinement for 1. 1 Formula
C104H152Cu12K4 Mo8N8O32S32
FW Temperature (K)
4739.10 150(2)
Wavelength (Å)
0.71073
Crystal system
tetragonal
Space group
I4(1)cd
a (Å)
27.766(4)
b (Å)
27.766(4)
c (Å)
42.695(8)
3
V (Å )
32916(9)
Z
8
Dc (Mg m-3)
1.913
-1
µ(mm )
2.670
F(000)
18875
Reflections collected
40919
Unique reflection
13364
Rint
0.0413
GOF on F2
1.062
R1 [I>2σ(I)]
0.0501
wR2 [I>2σ(I)]
0.1087
∆ρmax / ∆ρmin (e Å-3)
0.836 / -0.617
Table 2. Selected bond lengths (Å) for 1. Mo(1)-S(1)
2.109(3)
Mo(1)-S(3)
2.239(2)
Mo(1)-S(16)
2.248(2)
Mo(1)-S(2)
2.248(2)
Mo(2)-S(7)
2.170(3)
Mo(2)-S(4)
2.187(3)
Mo(2)-S(6)
2.196(2)
Mo(2)-S(5)
2.293(2)
Mo(3)-S(10)
2.123(3)
Mo(3)-S(8)
2.242(2)
Mo(3)-S(9)
2.244(2)
Mo(3)-S(11)
2.260(2)
Mo(4)-S(15)
2.182(2)
Mo(4)-S(14)
2.195(2)
Mo(4)-S(13)
2.198(2)
Mo(4)-S(12)
2.291(2)
Cu(1)-S(4)
2.292(3)
Cu(1)-S(3)
2.304(2)
Cu(1)-S(2)
2.308(2)
Cu(1)-S(5)
2.337(3)
Cu(2)-S(8)
2.304(3)
Cu(2)-S(5)
2.307(2)
Cu(2)-S(7)
2.327(3)
Cu(2)-S(9)
2.328(2)
Cu(3)-S(11)#1
2.276(2)
Cu(3)-S(6)
2.302(3)
Cu(3)-S(8)#1
2.331(3)
Cu(3)-S(5)
2.352(2)
Cu(4)-S(11)
2.304(2)
Cu(4)-S(13)
2.306(2)
Cu(4)-S(9)
2.319(3)
Cu(4)-S(12)
2.343(2)
Cu(5)-S(3)
2.296(2)
Cu(5)-S(14)#1
2.308(2)
Cu(5)-S(16)
2.326(2)
Cu(5)-S(12)#1
2.347(2)
Cu(6)-S(16)
2.300(2)
Cu(6)-S(12)
2.305(2)
Cu(6)-S(2)
2.310(2)
Cu(6)-S(15)
2.323(2)
Symmetry transformations used to generate equivalent atoms: #1 -x, -y, z
Table 3. Selected bond angles (º) for 1. S(1)-Mo(1)-S(3)
110.91(9)
S(1)-Mo(1)-S(16)
110.91(10)
S(3)-Mo(1)-S(16)
107.81(8)
S(1)-Mo(1)-S(2)
110.02(10)
S(3)-Mo(1)-S(2)
108.17(9)
S(16)-Mo(1)-S(2)
108.94(8)
S(7)-Mo(2)-S(4)
110.46(12)
S(7)-Mo(2)-S(6)
110.00(11)
S(4)-Mo(2)-S(6)
108.95(11)
S(7)-Mo(2)-S(5)
108.72(9)
S(4)-Mo(2)-S(5)
108.98(10)
S(6)-Mo(2)-S(5)
109.72(9)
S(10)-Mo(3)-S(8)
108.25(11)
S(10)-Mo(3)-S(9)
111.57(11)
S(8)-Mo(3)-S(9)
109.08(9)
S(10)-Mo(3)-S(11)
111.71(10)
S(8)-Mo(3)-S(11)
108.21(9)
S(9)-Mo(3)-S(11)
107.94(9)
S(15)-Mo(4)-S(14)
109.65(9)
S(15)-Mo(4)-S(13)
108.92(8)
S(14)-Mo(4)-S(13)
111.05(8)
S(15)-Mo(4)-S(12)
109.35(8)
S(14)-Mo(4)-S(12)
108.86(8)
S(13)-Mo(4)-S(12)
108.98(9)
S(4)-Cu(1)-S(3)
107.49(10)
S(4)-Cu(1)-S(2)
114.12(9)
S(3)-Cu(1)-S(2)
103.98(9)
S(4)-Cu(1)-S(5)
103.96(10)
S(3)-Cu(1)-S(5)
113.63(9)
S(2)-Cu(1)-S(5)
113.77(8)
S(8)-Cu(2)-S(5)
118.93(9)
S(8)-Cu(2)-S(7)
108.09(11)
S(5)-Cu(2)-S(7)
103.03(9)
S(8)-Cu(2)-S(9)
104.11(9)
S(5)-Cu(2)-S(9)
113.39(10)
S(7)-Cu(2)-S(9)
109.01(10)
S(11)#1-Cu(3)-S(6)
107.57(9)
S(11)#1-Cu(3)-S(8)#1
104.64(9)
S(6)-Cu(3)-S(8)#1
116.16(11)
S(11)#1-Cu(3)-S(5)
119.26(9)
S(6)-Cu(3)-S(5)
104.11(9)
S(8)#1-Cu(3)-S(5)
105.69(9)
S(11)-Cu(4)-S(13)
107.24(8)
S(11)-Cu(4)-S(9)
103.95(10)
S(13)-Cu(4)-S(9)
117.00(8)
S(11)-Cu(4)-S(12)
116.33(8)
S(13)-Cu(4)-S(12)
103.63(9)
S(9)-Cu(4)-S(12)
109.20(8)
S(3)-Cu(5)-S(14)#1
108.83(8)
S(3)-Cu(5)-S(16)
103.31(8)
S(14)#1-Cu(5)-S(16)
114.61(9)
S(3)-Cu(5)-S(12)#1
118.53(9)
S(14)#1-Cu(5)-S(12)#1
103.23(8)
S(16)-Cu(5)-S(12)#1
108.80(8)
S(16)-Cu(6)-S(12)
115.26(8)
S(16)-Cu(6)-S(2)
105.05(8)
S(12)-Cu(6)-S(2)
115.41(10)
S(16)-Cu(6)-S(15)
108.20(9)
S(12)-Cu(6)-S(15)
104.14(8)
S(2)-Cu(6)-S(15)
108.52(8)
Symmetry transformations used to generate equivalent atoms: #1 -x, -y, z
Table 4. The hyperpolarizability values (γ) of some representative heterothiometallic clusters measured at 532 nm. Compound
Structure type
γ (esu)
Ref.
1
supra-cubane-like
1.5×10-30
this work
[Et4N]4[Mo4O4S12Cu8{(Ph2PS)2 N}4]
dodecanuclear square
1.81×10-30
14
{[Sr(DMAC)6 ]2[Mo4 S16Ag4]}
octanuclear square-like
2.13×10-30
15
[Et4N]2[MoS4Cu4(SCN)4(2-pic)4]
planar open shape
1.29×10-31
29
[MoS4Cu4Br2(py)6 ]
planar open shape
1.17 × 10-30
30
[MoOS3Cu3(4-pic)6]· BF4
nest-shape
2.89×10-31
31
[Et4 N]3[MoOS3(µ3-I)(AgI)3]
cubane-like
9.07×10-31
32
A unique anionic octameric supra-cubane-like heterothiometallic Mo/S/Cu cluster was synthesized in the presence of potassium-crownether host-guest cation. Furthermore, Z-scan studies reveal that this cluster possesses effective third-order nonlinear optical properties.