杂双金属硫属原子簇聚合物的合成、结构及三阶非线性光学性质
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摘要
本文主要研究了Mo(W)／S／Cu(Ag)原子簇聚合物的合成和结构，共合成和结构表征了14个未见文献报道的Mo(W)／S／Cu(Ag)原子簇聚合物，其中零维聚合物2个，一维聚合物8个，三维聚合物4个。还合成和结构表征了1个新的单体Mo／S／Ag原子簇化合物。并对其中部分化合物进行了三阶非线性光学性质的研究。
1．研究了硫代金属酸盐[MO_nS_(4-n)]~(2-)(M=Mo、W，n=0、1)和Cu_2S在四甲基铵盐和四正丁基铵盐为结构诱导剂条件下的反应，获得了两个零维原子簇聚合物，分别具有三核线形和新颖的十三核8字形双环结构，后一结构未见文献报道。
2．使用几种不同的结构诱导剂，进行了[NH_4]_2[MS_4]和Ag~+离子的自组装反应，获得了7个一维Mo(W)／S／Ag原子簇聚合物，分属三种不同的构型，分别为直链形，“1：2”阶梯状锯齿链形和“2：2”阶梯状锯齿链形。后两种构型未见报道。
3．通过比较、分析一些一维Mo(W)／S／Ag原子簇聚合物和文献报道的类似化合物的合成反应条件与晶体结构，指出配阳离子的价态、半径、配阳离子中配体的取向，结晶溶剂以及共存阴离子都可能影响聚合物链的构型，并对这些影响作了较为深入的分析。其中共存阴离子进入产物，进而对产物中阴离子链构型产生影响未见文献报道。
4．研究了以4，4′-联吡啶桥联的一维W／S／Cu原子簇聚合物的合成和晶体结构，探讨了二步法中中间体的选择和聚合产物维数或聚合度的关系。
5．从拓扑连接的角度分析了已知Mo(W)／S／Cu(Ag)原子簇聚合物的结构，指出提高节点的连接数是获得三维结构的重要途径；分析了卤素配体以及平衡阳离子对产物聚合度的影响。在以上分析的基础上，分别研究了[NH_4]_2[MOS_3]-CuCN-[Me_4N]NO_3和[NH_4]_2[MOS_3]-CuCN-4，4′-联吡啶两种反应体系，获得了4个三维原子簇聚合物。[MOS_3]~(2-)衍生物至今尚无三维结构的报道。其中两个化合物的阴离子簇骨架具有新颖的“ACS”拓扑结构，并具有特殊的双重包含结构。就我们所知，在原子簇聚合物以及配位聚合物中，这种特殊的包含结构未见文献报道。另两个化合物的阴离子簇骨架呈现为一种柱撑式三维结构，具有金刚石型拓扑结构。
6．对部分合成的簇合物进行了非线性光学性质测试。其中两个含端氧基的中性类立方烷构型的簇合物具有显著的三阶非线性光学性质，这与文献报道的含端硫的中性类立方烷构型的簇合物没有可观测的三阶非线性光学性质不同；三个一维Mo(W)／S／Cu(Ag)原子簇聚合物也表现出较强的三阶NLO行为，其中两个化合物的二阶超极化率γ高出已报道的同类化合物约一个数量级；在合成的四个三维聚合物中有两个具有较强或强的三阶非线性光学性质。
The dissertation focuses on the syntheses and structures of polymericMo(W)/S/Cu(Ag) clusters, fourteen new Mo(W)/S/Cu(Ag) polymers being prepared andstructurally characterized, of which two are 0-D, eight are 1-D, and four are 3-Dpolymers. Besides one new monomer of Mo/S/Ag cluster was also synthesized andstructurally characterized. The third-order nonlinear optic (NLO) properties of somesynthesized compounds were investigated.
1. The reactions of [MO_nS_(4-n)]~(2-) (M=Mo, W; n=0,1) with CUES in the presence of[Me_4N]~+ or [n-Bu_4N]~+ as structure-inducer resulted in two 0-D polymeric clusters, withtrinuclear linear and novel tridecanuclear double-ring structure, respectively. The latterstructural pattern has not been observed in literatures.
2. The reactions of [NH_4]_2[MS_4] with Ag~+ induced by several different templatesled to the formation of seven 1-D Mo(W)/S/Ag polymers, of which three configurationswere found, namely linear chain, zigzag chain with '1:2' steps, and zigzag chain with'2:2' steps. The last two configurations have not been reported thus far.
3. By comparing the reactive conditions and crystal structures among some 1-DMo(W)/S/Ag clusters and known analogs, it has been pointed out that the valences andradii of cationic complexes, the orientation of ligands in cationic complexes, crystallizedsolvents, and coexisting anions can all exert influences on the configurations ofpolymeric chains. These influences were analyzed in some depth. The inclusion ofcoexisting anions and its impact on polymeric configuration have not been observed inthis system before.
4. The synthesis and crystal structure of a 1-D W/S/Cu cluster bridged by4,4'-bipyridyl were studied and the correlation between the intermediate compound intwo-step reaction and the dimensionality of resulting products was also analyzed.
5. The structures of some known Mo(W)/S/Cu(Ag) polymers were analyzed from atopological connection view and augmenting the connectivity of net-nodes was pointedout as an important approach to 3-D structures. The effects of halogens andcomplementary cations on the dimensionality of resulting products were also discussed.Based on these discussion, two reaction systems of [NH_4]_2[MOS_3]-CuCN-[Me_4N]NO_3and [NH_4]_2[MOS_3]-CuCN-4,4'-bipyridyl were studied to give four 3-D polymericclusters with [MOS_3] moieties, no such [MOS_3]~(2-) derivatives with 3-D structures beingreported to date. Two of the four 3-D clusters were found to possess novel ACS topologyin their anionic skeletons, and furthermore, a special two-folded inclusion is observed in these two clusters, which, to our knowledge, has not been reported in the domains ofpolymeric clusters and coordination polymers. Another two clusters assume a pillared3-D structure, with diamond topology.
6. The third-order NLO properties of some synthesized clusters were investigated.Among them two neutral cubane-like clusters with terminal oxygen exhibit notablethird-order NLO properties as against no observable NLO effects found for reportedanalogs with terminal sulfur. Three 1-D Mo(W)/S/Ag polymers also show strongthird-order NLO properties, two of them having a higher secondary hyperpolarisabilityabout ten times larger than that of the reported 1-D W/S/Ag cluster. Of the foursynthesized 3-D clusters, two were found to display moderate and strong third-orderNLO properties, respectively.
1．研究了硫代金属酸盐[MO_nS_(4-n)]~(2-)(M=Mo、W，n=0、1)和Cu_2S在四甲基铵盐和四正丁基铵盐为结构诱导剂条件下的反应，获得了两个零维原子簇聚合物，分别具有三核线形和新颖的十三核8字形双环结构，后一结构未见文献报道。
2．使用几种不同的结构诱导剂，进行了[NH_4]_2[MS_4]和Ag~+离子的自组装反应，获得了7个一维Mo(W)／S／Ag原子簇聚合物，分属三种不同的构型，分别为直链形，“1：2”阶梯状锯齿链形和“2：2”阶梯状锯齿链形。后两种构型未见报道。
3．通过比较、分析一些一维Mo(W)／S／Ag原子簇聚合物和文献报道的类似化合物的合成反应条件与晶体结构，指出配阳离子的价态、半径、配阳离子中配体的取向，结晶溶剂以及共存阴离子都可能影响聚合物链的构型，并对这些影响作了较为深入的分析。其中共存阴离子进入产物，进而对产物中阴离子链构型产生影响未见文献报道。
4．研究了以4，4′-联吡啶桥联的一维W／S／Cu原子簇聚合物的合成和晶体结构，探讨了二步法中中间体的选择和聚合产物维数或聚合度的关系。
5．从拓扑连接的角度分析了已知Mo(W)／S／Cu(Ag)原子簇聚合物的结构，指出提高节点的连接数是获得三维结构的重要途径；分析了卤素配体以及平衡阳离子对产物聚合度的影响。在以上分析的基础上，分别研究了[NH_4]_2[MOS_3]-CuCN-[Me_4N]NO_3和[NH_4]_2[MOS_3]-CuCN-4，4′-联吡啶两种反应体系，获得了4个三维原子簇聚合物。[MOS_3]~(2-)衍生物至今尚无三维结构的报道。其中两个化合物的阴离子簇骨架具有新颖的“ACS”拓扑结构，并具有特殊的双重包含结构。就我们所知，在原子簇聚合物以及配位聚合物中，这种特殊的包含结构未见文献报道。另两个化合物的阴离子簇骨架呈现为一种柱撑式三维结构，具有金刚石型拓扑结构。
6．对部分合成的簇合物进行了非线性光学性质测试。其中两个含端氧基的中性类立方烷构型的簇合物具有显著的三阶非线性光学性质，这与文献报道的含端硫的中性类立方烷构型的簇合物没有可观测的三阶非线性光学性质不同；三个一维Mo(W)／S／Cu(Ag)原子簇聚合物也表现出较强的三阶NLO行为，其中两个化合物的二阶超极化率γ高出已报道的同类化合物约一个数量级；在合成的四个三维聚合物中有两个具有较强或强的三阶非线性光学性质。
The dissertation focuses on the syntheses and structures of polymericMo(W)/S/Cu(Ag) clusters, fourteen new Mo(W)/S/Cu(Ag) polymers being prepared andstructurally characterized, of which two are 0-D, eight are 1-D, and four are 3-Dpolymers. Besides one new monomer of Mo/S/Ag cluster was also synthesized andstructurally characterized. The third-order nonlinear optic (NLO) properties of somesynthesized compounds were investigated.
1. The reactions of [MO_nS_(4-n)]~(2-) (M=Mo, W; n=0,1) with CUES in the presence of[Me_4N]~+ or [n-Bu_4N]~+ as structure-inducer resulted in two 0-D polymeric clusters, withtrinuclear linear and novel tridecanuclear double-ring structure, respectively. The latterstructural pattern has not been observed in literatures.
2. The reactions of [NH_4]_2[MS_4] with Ag~+ induced by several different templatesled to the formation of seven 1-D Mo(W)/S/Ag polymers, of which three configurationswere found, namely linear chain, zigzag chain with '1:2' steps, and zigzag chain with'2:2' steps. The last two configurations have not been reported thus far.
3. By comparing the reactive conditions and crystal structures among some 1-DMo(W)/S/Ag clusters and known analogs, it has been pointed out that the valences andradii of cationic complexes, the orientation of ligands in cationic complexes, crystallizedsolvents, and coexisting anions can all exert influences on the configurations ofpolymeric chains. These influences were analyzed in some depth. The inclusion ofcoexisting anions and its impact on polymeric configuration have not been observed inthis system before.
4. The synthesis and crystal structure of a 1-D W/S/Cu cluster bridged by4,4'-bipyridyl were studied and the correlation between the intermediate compound intwo-step reaction and the dimensionality of resulting products was also analyzed.
5. The structures of some known Mo(W)/S/Cu(Ag) polymers were analyzed from atopological connection view and augmenting the connectivity of net-nodes was pointedout as an important approach to 3-D structures. The effects of halogens andcomplementary cations on the dimensionality of resulting products were also discussed.Based on these discussion, two reaction systems of [NH_4]_2[MOS_3]-CuCN-[Me_4N]NO_3and [NH_4]_2[MOS_3]-CuCN-4,4'-bipyridyl were studied to give four 3-D polymericclusters with [MOS_3] moieties, no such [MOS_3]~(2-) derivatives with 3-D structures beingreported to date. Two of the four 3-D clusters were found to possess novel ACS topologyin their anionic skeletons, and furthermore, a special two-folded inclusion is observed in these two clusters, which, to our knowledge, has not been reported in the domains ofpolymeric clusters and coordination polymers. Another two clusters assume a pillared3-D structure, with diamond topology.
6. The third-order NLO properties of some synthesized clusters were investigated.Among them two neutral cubane-like clusters with terminal oxygen exhibit notablethird-order NLO properties as against no observable NLO effects found for reportedanalogs with terminal sulfur. Three 1-D Mo(W)/S/Ag polymers also show strongthird-order NLO properties, two of them having a higher secondary hyperpolarisabilityabout ten times larger than that of the reported 1-D W/S/Ag cluster. Of the foursynthesized 3-D clusters, two were found to display moderate and strong third-orderNLO properties, respectively.
引文
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