Syntheses, Structures And Characterizations Of Copper/Zinc Complexes Based On Carboxylate、Sulfonate Ligands

Transition metal complexes with diverse structures have attracted increasing attention in the field of chemistry due to their applications in the field of optics, electricity, magnetism, catalysis, ion exchange, biological modeling and molecular sieve adsorption.In this dissertation, ten novel compounds have been synthesized by using carboxylate, sulfonate and nitrogenous heterocyclic ligands with copper or zinc ions. The study on synthetic conditions and rules for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new compounds are also carried out. In addition, the fluorescence and nonlinear optical properties of partial compounds have been preliminary explored. These compounds have been structurally characterized by elemental analyses, Infrared spectra, thermal analysis and single crystal X-ray diffractions. The specific research contents can be summarized as follows:Three novel copper(Ⅱ) and zinc(Ⅱ) compounds{[CuL(bpe)0.5]·4H2O}n (1),{[ZnL(bibp)]·DMA·(H2O)2}n (2) and{ZnL(bix)0.5}n (3) have been synthesized under hydrothermal conditions through the reaction of "V" shaped dicarboxylic acid ligand:4,4’-(phenylazanediyl)dibenzoic acid (H2L) and different nitrogenous heterocyclic complexes as auxiliary ligands with copper and zinc ions. Compounds1and3contain the building block units [Cu2(CO2)4] and [Zn2(CO2)4] respectively, which are linked by L2-and auxiliary ligands at two different axial position, thus leading to2D layers. The topological analysis of compound1displays schlafli symbol{44·610·8}. Compound2is a2D structure with{65·8} net resulted from L2-and auxiliary ligands linking with the neighboring Zn atoms.Four novel copper(Ⅱ) compounds constructed with three different sulfonic acid ligands (4-hydroxypyridone-3-sulfonic acid, quinoline-8-sulfonic acid and8-hydroxy-5-quinolinesulfonic acid) were obtained by hydrothermal methods or reflux methods, including:[Cu(OPS)(phen)Br]·H2O (4),[Cu(L1)2H2O]·H2O (5),{Cu(2,2’-bpy)(SO4)(H2O)2}n (6) and {[Cu(HQS)2]·(4,4’-bpy)-3H2O}n (7). Compounds4and5possess discrete structures, while compounds6and7show1D chains. Compounds4～7formed3D supramolecular network through hydrogen bonding and π-π stacking.Three kinds of copper(Ⅰ) and zinc(Ⅱ) compounds based on nitrogenous heterocyclic ligands have been hydrothermally synthesized, including:[Cu(phen)2Cl]·9H2O (8),[ZnCl2(3,5-lut)2](9) and [Zn2Cl4(3-etpy)4](10). Interestingly, complex8contains one-dimensional helical water cluster chains, which has important significance for the further study of water clusters. Complexes9and10have the same coordination mode. The Zn has a distorted N2Cl2tetrahedral environment constructed by two nitrogen atoms from3,5-lut or3-etpy ligands and two chloride ions from ZnCl2.