摘要
本论文基于晶体工程学原理,从有机配体的设计与合成出发,研究了有机配体对于配位聚合物最终结构的影响及金属离子的配位数对于最终结构和维数的影响,总结了不同有机配体和金属离子在构筑配位聚合物中所起到的不同作用,丰富了配位聚合物的种类与结构,为开发具有功能特性的晶态材料提供了实验数据。本论文选择1,2,4-三氮唑及其衍生物作为含氮配体,选用不同构型,不同结构的多齿羧酸作为含氧配体,合成出25种配位聚合物,并对所合成的配合物进行了单晶结构测试与解析,以及相关功能性质的研究与探讨。
1、以1,2,4-三氮唑为含氮有机配体和不同的多齿羧酸配体,与d10金属Zn和Cd离子反应,在水热反应条件下,构筑了9个具有不同结构和不同维数的新型配位聚合物。配合物1和2是由1,2,4-三氮唑与Zn或Cd离子构筑的三维网络结构,配合物3-9都是由d10金属和1,2,4-三氮唑及多齿羧酸类配体构筑的三维网络配合物,其中配合物9是一个三维手性配合物。[Zn2(TRZ)4(HTRZ)2]n(1)[Cd2(TRZ)3I]n(2){[Zn2(TRZ)(pBDC)1.5H2O].(H2O)4)n(3){[Cd2(TRZ)(pBDC)1.5H2O]·(H2O)0.5}n(4){[Zn(TRZ)(mHBDC)H2O].(H2O)4}n(5){[Zn5(TRZ)4(BTC)2H2O2]·(H2O)6)n(6)([Zn6(TRZ)6(HOBA)2(OBA)2]·(H2O)7]n(7){[Cd3(TRZ)2(OBA)2]·(H2O)0.5}n(8){Cd(TRZ)2(PZDC)0.5}n(9)
2、以1,2,4-三氮唑衍生物为含氮有机配体结合不同的多齿羧酸配体,与d10金属Zn和Cd离子反应,在水热反应条件下,构筑了10个具有不同结构,不同维数的新型配位聚合物。配合物17是一维链状结构,配合物12和15是一维纳米管型结构,配合物13、14、18是二维层结构,配合物11、16、19是复杂的三维结构。研究结果表明,三氮唑配体的引入有助于辅助合成不同维数的复杂结构配合物,不同的有机配体对于最终产物的维度和结构起着至关重要的决定性作用。[Zn(L1)2(pBDC)·H2O]n(10)[Cd(L1)(pBDC)·3H2O]n(11)[Zn(L1)2(mBDC)·0.5H2O]n(12)[Cd(L1)(mBDC)·2H2O]n(13)[Zn(L1)2(BTC)·3.5H2O]n(14)[Cd(L1)2(BTC)·2H2O]n(15)[Zn2(L1)(PMA)·3H2O]n(16)[Zn(L2)2(pBDC)1(pBDC)0.5](17)[Zn(L2)2(mBDC)·3H O]n(18)[Cd(Lz)2(pBDC)(pBDC)0.5·3H2O]n(19)
3、以丙氨酸衍生物为多齿羧酸配体,通过选择不同的含氮有机配体,与不同的过渡金属离子反应,在水热条件下合成出6个具有不同维数不同结构类型的配位聚合物。其中配合物20是一个具有22元环结构的单分子配合物,配合物21和22是由Cd离子构筑的三维微孔配合物,配合物23是由5核Cd簇构筑的三维8连接并具有hex拓扑的三维网络,配合物24具有折叠形状的二维层结构,配合物25则是一个具有三重互穿的三维3,4连接网络配合物。配合物的光化学性质显示,这些新颖配合物可能是潜在的光学材料。[Zn2(L1)2phen2(H2O)2](20)[Cd3(L1)2(OH)2(4,4'-bpy)(H2O)2]·2H2O(21)[Co3(L1)2(OH)2(4,4'-bpy)(H2O)2]·2H2O(22)[Cd5(L1)2(OH)2(trz)4(L3)]·2H2O(23)[Zn(HL2)(4,4'-bpy)](24)[Cd3(L2)2(L3)2(H2O)5]·H2O(25)
The aim of this thesis is to synthesize new coordination polymers on the basis of1,2,4-triazole ligands and their derived ligands and different multicarboxylate ligands, to explore the synthetic conditions and rules for these compounds, analysis influence of organic ligands and metal ions on the formation of final structures, and to study the relationships between structures and properties for these new coordination polymers. In this thesis,25new coordination polymers were synthesized under the hrdrothermal condition, and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions.
1. Nine new coordination complexes have been synthesized on the basis of1,2,4-triazole ligand and different multicarboxylate ligands with d10metal ions under the hydrothermal condition with different structures. Complexes1and2are three-dimensional networks constructed by1,2,4-triazole ligand and Zn or Cd ions; complexes3-9are three dimension networks based on1,2,4-triazole and different multicarboxylate ligands with different structures. In addition, compound9is a three dimensional chiral network.[Zn2(TRZ)4(HTRZ)2]n(1)[Cd2(TRZ)3I]n(2){[Zn2(TRZ)(pBDC)1.5H2O]·(H2O)4}n(3){[Cd2(TRZ)(pBDC)1.5H2O]·(H2O)0.5}n(4){[Zn(TRZ)(mHBDC)H2O]·(H2O)4}n(5){[Zn5(TRZ)4(BTC)2H2O2]·(H2O)6}n(6){[Zn6(TRZ)6(HOBA)2(OBA)2]·(H2O)7}n(7){[Cd3(TRZ)2(OBA)2]·(H2O)0.5}n(8){Cd(TRZ)2(PZDC)0.5}n(9)
2. Ten new coordination complexes have been synthesized on the basis of derivant of1,2,4-triazole ligand and different multicarboxylate ligands with Zn and Cd ions under the hydrothermal condition with different dimensional structures. Complexes17is one-dimensional chain structure; compound12and15are one-dimensional nanotube like structures; complexes13,14and18are two-dimensional layer structures and compounds11,16,19are three-dimensional networks. The structures of these complexes present that the1,2,4-triazole ligand are very helpful for the formation of coordination complexes with different dimensional structures, and the difference of organic ligands have important effective on the final structures.[Zn(L1)2(pBDC)·H2O]n(10)[Cd(L1)(pBDC)·3H2O]n(11) [Zn(L1)2(mBDC)·0.5H2O]n(12)[Cd(L1)(m B D C)·2H2O]n(13)[Zn(L1)2(BTC)·3.5H2O]n(14)[Cd(L1)2(BTC)·2H2O]n(15)[Zn2(L1)(PMA)·3H2O]n(16)[Zn(L2)2(pBDC)1(pBDC)0.5](17)[Zn(L2)2(mBDC)·3H2O]n(18)[Cd(L2)2(pBDC)(pBDC)0.5·3H2O]n(19)
3. Six new coordination complexes have been synthesized on the basis of derivant of alanine and different N-containing ligands with transition metal ions under the hydrothermal condition with different dimensional structures. Complexes20is isolated22-membered ring; compound21and22are one-dimensional micropore structures; complexes23is three-dimensional structures with hex topology based on the pentanuclear Cd cluster, compound24is two-dimensional layer structures and compound25is three-dimensional networks with three-fold interpenation. These compounds have the potential to be optical materials.[Zn2(L1)2phen2(H2O)2](20)[Cd3(L1)2(OH)2(4,4'-bpy)(H2O)2]·2H2O(21)[Co3(L1)2(OH)2(4,4'-bpy)(H2O)2]·2H2O(22)[Cd5(L1)2(OH)2(trz)4(L3)]·2H2O(23)[Zn(HL2)(4,4'-bpy)](24)[Cd3(L2)2(L3)2(H2O)5]·H2O(25)
引文
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