V（Mo，W）-Cu（Ag）-S簇合物的合成及其三阶非线性光学性质的研究
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摘要
论文主要研究了V(Mo,W)-Cu(Ag)-S簇合物的合成反应和结构特征,并首次对V-Cu-S化合物进行了光学性质测试,其目的在于寻找具有更强的三阶非线性光学性能的光学分子功能材料。
实验合成了多个具有不同骨架结构的原子簇化合物:V_2S_6O_2Cu_6(3-MePy)_61; VS_4(μ3-I)(CuPPh_3)_4 2; MoOS_3(μ3-Br)Ag_3(PPh_3)_3 3; [Et_4N]_n[WS_4Ag]_n 4; [MoOS_3Cu_3I(C_7H_9N)_2]_2 5; (Bu_4N)_3[WOS_3Cu_3(NCS)_3]I 6; (Bu_4N)_3[MoOS_3Cu_3(NCS)_3]I 7以及以SCN和吡啶作为混合配体的簇合物8。其中簇合物1、2、3的晶体结构已经通过单晶X射线衍射法确定。采用SHELXTL程序对数据进行处理得到各簇合物的晶胞参数分别为:a=9.756(2)(?),b=10.422(2)(?),c=11.937(2)(?),α=108.32(3)°,β=98.11(3)°,γ=99.38(3)°,Z=2,R_1=0.0327,wR_2=0.0728(1);a=11.916(2)(?),b=13.247(3)(?),c=22.511(5)(?),α=91.75(3)°,β=99.09(3)°,γ=116.04(3)°,Z=2,R_1=0.1064,wR_2=0.2838(2);a=15.736(3)(?),b=11.193(2)(?),c=30.357(6)(?),α=90°,β=98.11(3)°,γ=90°,Z=4,R_1=0.0955,wR_2=0.1591(3);其他化合物的可能结构或组成均通过红外光谱、元素分析结果和已报道的同系物推断得出。
对簇合物1和2的非线性光学性质的测试结果表明它们具有较强的三阶非线性光学性质。在DMF溶液中测得化合物1(1.58×10~(-4)mol/dm~3)和2(1.24×10~(-4)mol/dm~3)的三阶非线性吸收系数α_2值分别为3.5×10~(-10)m/W1和1.7×10~(-10)m/W2;三阶非线性折射系数n_2值如下:1.27×10~(-18)m~2/W1和-6.86×10~(-19)m~2/W2。三阶非线性磁化率x~(3)值分别为1.2×10~(-11)esu1和5.9×10~(-12)esu2而相应的超极化率γ分别为4.2×10~(-32)esu1和1.6×10~(-32)esu2。通过n_2数值的正负推测出化合物1和2分别显示较强的自聚焦和自散焦作用。比较这两个化合物,推测骨架的对称性、重金属原子的个数以及结构的刚性应当是造成非线性光学性质出现差异的主要原因。
The thesis focuses on studies of synthetic reactions and structural characterizations of V(Mo, W)-S-Cu(Ag) clusters and optical properties of V-S-Cu species.Several new cluster compounds with different skeletons were synthesized. V_2S_6O_2Cu_6(3-MePy)_6 1; VS_4(μ3-I)(CuPPh_3)_4 2; MoOS_3(μ_3-Br)Ag_3(PPh_3)_3 3;[Et_4N]_n[WS_4Ag]_n 4; [MoOS_3Cu_3I(C_7H_9N)_2]_2 5; (Bu_4N)_3[WOS_3Cu_3(NeS)_3]I 6; (Bu_4N)_3[MoOS_3Cu_3(NCS)_3]I 7 and cluster 8 (Py, SCN-ligand). Three structures were determined by Single-crystal X-ray diffraction. The collected data is given: a = 9.756(2) A, b = 10.422(2) A, c = 11.937(2) A, α = 108.32(3) °,β = 98.11(3)°, γ = 99.38(3)°, Z = 2, R_1 = 0.0327, wR_2 = 0.0728 (1) ; a = 11.916(2) A, b = 13.247(3) A, c = 22.511(5) A, α = 91.75(3) °, β = 99.09(3) °, γ = 116.04(3) °, Z = 2 , R_1 = 0.1064, wR_2 = 0.2838(2); a=15.736(3)A, b=11.193 (2) A, c=30.357(6) A, α=90 °, β=98.11(3)°, γ=90°, Z=4, R_1 = 0.0955, wR_2 =0.1591(3). The structures or molecule formulas of other compounds were deduced from the reported homologues by their IR spectra and elemental analyses.The third-nonlinear optical (NLO) properties of cluster 1 and 2 were investigated with an 8ns pulsed laser at 532nm. These two clusters exhibit moderately strong third-order NLO absorption effects [α_2= 3.5×10~(-10)m/W 1, 1.7×10~(-10) m/W 2] and self-focusing or self-defocusing performance in 1.58×10~(-4)mol/dm~3 1 and 1.24×10~(-4) mol/dm~3 2 DMF solution. The third-order NLO refractive coefficients (n_2) of cluster 1 and 2 are 1.27 × 10~(-18) m~2/W and -6.86 × 10~(-19) m~2/W, respectively. The corresponding effective NLO susceptibilities x~((3)) are calculated to be 1.2×10~(-11)esu 1 and 5.9×10~(-12) esu 2, white the hyperpolarizabilities y to be 4.2×10~(-32)esu 1 and 1.6×10~(-32)esu 2. Based on the NLO experimental results, it can be drawn that the symmetry of skeleton, the number of heavy atoms and the rigidity of structures are the main reasons for the differences in NLO properties.
实验合成了多个具有不同骨架结构的原子簇化合物:V_2S_6O_2Cu_6(3-MePy)_61; VS_4(μ3-I)(CuPPh_3)_4 2; MoOS_3(μ3-Br)Ag_3(PPh_3)_3 3; [Et_4N]_n[WS_4Ag]_n 4; [MoOS_3Cu_3I(C_7H_9N)_2]_2 5; (Bu_4N)_3[WOS_3Cu_3(NCS)_3]I 6; (Bu_4N)_3[MoOS_3Cu_3(NCS)_3]I 7以及以SCN和吡啶作为混合配体的簇合物8。其中簇合物1、2、3的晶体结构已经通过单晶X射线衍射法确定。采用SHELXTL程序对数据进行处理得到各簇合物的晶胞参数分别为:a=9.756(2)(?),b=10.422(2)(?),c=11.937(2)(?),α=108.32(3)°,β=98.11(3)°,γ=99.38(3)°,Z=2,R_1=0.0327,wR_2=0.0728(1);a=11.916(2)(?),b=13.247(3)(?),c=22.511(5)(?),α=91.75(3)°,β=99.09(3)°,γ=116.04(3)°,Z=2,R_1=0.1064,wR_2=0.2838(2);a=15.736(3)(?),b=11.193(2)(?),c=30.357(6)(?),α=90°,β=98.11(3)°,γ=90°,Z=4,R_1=0.0955,wR_2=0.1591(3);其他化合物的可能结构或组成均通过红外光谱、元素分析结果和已报道的同系物推断得出。
对簇合物1和2的非线性光学性质的测试结果表明它们具有较强的三阶非线性光学性质。在DMF溶液中测得化合物1(1.58×10~(-4)mol/dm~3)和2(1.24×10~(-4)mol/dm~3)的三阶非线性吸收系数α_2值分别为3.5×10~(-10)m/W1和1.7×10~(-10)m/W2;三阶非线性折射系数n_2值如下:1.27×10~(-18)m~2/W1和-6.86×10~(-19)m~2/W2。三阶非线性磁化率x~(3)值分别为1.2×10~(-11)esu1和5.9×10~(-12)esu2而相应的超极化率γ分别为4.2×10~(-32)esu1和1.6×10~(-32)esu2。通过n_2数值的正负推测出化合物1和2分别显示较强的自聚焦和自散焦作用。比较这两个化合物,推测骨架的对称性、重金属原子的个数以及结构的刚性应当是造成非线性光学性质出现差异的主要原因。
The thesis focuses on studies of synthetic reactions and structural characterizations of V(Mo, W)-S-Cu(Ag) clusters and optical properties of V-S-Cu species.Several new cluster compounds with different skeletons were synthesized. V_2S_6O_2Cu_6(3-MePy)_6 1; VS_4(μ3-I)(CuPPh_3)_4 2; MoOS_3(μ_3-Br)Ag_3(PPh_3)_3 3;[Et_4N]_n[WS_4Ag]_n 4; [MoOS_3Cu_3I(C_7H_9N)_2]_2 5; (Bu_4N)_3[WOS_3Cu_3(NeS)_3]I 6; (Bu_4N)_3[MoOS_3Cu_3(NCS)_3]I 7 and cluster 8 (Py, SCN-ligand). Three structures were determined by Single-crystal X-ray diffraction. The collected data is given: a = 9.756(2) A, b = 10.422(2) A, c = 11.937(2) A, α = 108.32(3) °,β = 98.11(3)°, γ = 99.38(3)°, Z = 2, R_1 = 0.0327, wR_2 = 0.0728 (1) ; a = 11.916(2) A, b = 13.247(3) A, c = 22.511(5) A, α = 91.75(3) °, β = 99.09(3) °, γ = 116.04(3) °, Z = 2 , R_1 = 0.1064, wR_2 = 0.2838(2); a=15.736(3)A, b=11.193 (2) A, c=30.357(6) A, α=90 °, β=98.11(3)°, γ=90°, Z=4, R_1 = 0.0955, wR_2 =0.1591(3). The structures or molecule formulas of other compounds were deduced from the reported homologues by their IR spectra and elemental analyses.The third-nonlinear optical (NLO) properties of cluster 1 and 2 were investigated with an 8ns pulsed laser at 532nm. These two clusters exhibit moderately strong third-order NLO absorption effects [α_2= 3.5×10~(-10)m/W 1, 1.7×10~(-10) m/W 2] and self-focusing or self-defocusing performance in 1.58×10~(-4)mol/dm~3 1 and 1.24×10~(-4) mol/dm~3 2 DMF solution. The third-order NLO refractive coefficients (n_2) of cluster 1 and 2 are 1.27 × 10~(-18) m~2/W and -6.86 × 10~(-19) m~2/W, respectively. The corresponding effective NLO susceptibilities x~((3)) are calculated to be 1.2×10~(-11)esu 1 and 5.9×10~(-12) esu 2, white the hyperpolarizabilities y to be 4.2×10~(-32)esu 1 and 1.6×10~(-32)esu 2. Based on the NLO experimental results, it can be drawn that the symmetry of skeleton, the number of heavy atoms and the rigidity of structures are the main reasons for the differences in NLO properties.
引文
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2 Holm R H. Metal Clusters in Biology: Quest for a Synthetic Representation of the Catalytic Site ofNitrogenase. Chem. Soc. Rev., 1981, 10: 455～490
3 ChiZhang et al. Studies on Two Interesting Microporous Polymeric Clusters {[Et_4N]_2[MS_4Cu_4(CN)_4]}_n(M=Mo, W) with Three-Dimensional Open Frameworks: Synthesis, Structural Characterization, Strong Optical Nonlinear-Linearities and Large Optical Limiting Properties. J. Chem. Soc., Dalton Trans., 2000: 2823～2829
4 Zheng Fakun et al. Synthesis and Crystal Structure of an Oeta-Nuelear V-Cu-S Cluster: [VS_3O(CttPBu_3)_2(CuSPBu_3)]_2. Chin J. Struct. Chem., 1997, 16(5): 365～370
5 Hong-wei Hou, Xin-Quan Xin, Shu Shi. Mo(W, V)-Cu(Ag)-S(Se) Cluster Compounds. Coordination Chemistry Reviews., 1996(153): 25～56
6 H. Q. Liu et al. Syntheses and Structural Characterizations of A Series of Mo(W)-Cu-S Compounds of Bidentate Dialkyldithiocarbamate Ligands. Crystal Structure of [NEt_4]_2[Mo_2Cu_5S_6O_2(Me_2NCS_2)]_3. J. Chem. Soc., Dalton Trans., 1990, 1: 1023～1025
7 S. W. Du et al. Designed Synthesis, Structure and Characterization of a Novel Double Cubane-Like Molybdenum-Copper-Sulphur Complex, {Mo_2Cu_6S_6[SCH_2CH_2OH]_2}(O)_2{PPh_3}_4. Polyhedron., 1992, 19: 2495～2500
8 H. W. Hou et al. Synthesis, Crystal Struture and Non-linear Optical Properties of [NEt_4]_4[Cu_6Mo_2S_6O_2Br_2I_4]~+. J. Chem. Soc., Dalton Trans., 1994, 1: 3211～3214
9 Y. Do, E. D. Simhon, R. H. Holm. Derivatives of Tetrathiovanadate(Ⅴ): Synthesis of the Linear Heterometallic Fe(μ_2-S)_2V(μ_2-S)_2Fe Core and the Structures of [VS_4]~(3-) and [VFe_2S_4Cl_4]~(3-). J. Am. Chem. Soc., 1983, 105: 6731～6732
10 A. Muller et al. (PPh_3)_4Cu_3(VS_4), ein neuartiger Thiovanadato Komplex mit T-formiger Anordnung der Metall-Atome. Z. anorg. allg. chem., 1987, 544: 107～144
11 Femando Canales et al. Heterobimetallic Complexes of Gold(Ⅰ) with the Tetrathiovanadate Anion. Crystal Structure of [VS_4(AuPPh_3)_2{Au(PPh_3)_2}]. Inorg. Chem., 1998, 37: 5376～5379
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