新型配合物[Cu_2(phen)_2(OH)_2(H_2O)_2][Cu_2(phen)_2(OH)_2Cl_2]Cl_2·6H_2O的合成与性质研究

Studies on the Synthesis and Properties of a Novel Complex [Cu_2(phen)_2(OH)_2(H_2O)_2][Cu_2(phen)_2(OH)_2Cl_2]Cl_2·6H_2O

采用溶液法合成了分子式为[Cu2(phen)2(OH)2(H2O)2][Cu2(phen)2(OH)2Cl2]Cl2.6H2O的配合物。通过元素分析、红外光谱、紫外光谱和X-射线单晶衍射对配合物进行了表征;此外,还对该配合物进行了非等温热分解动力学研究。研究表明,配合物中有两组双核配位单元,分别为[Cu2(phen)2(OH)2(H2O)2]2+和[Cu2(phen)2(OH)2Cl2];两个配位单元的中心原子铜均为五配位的,具有扭曲的四方锥结构,配合物通过氢键作用形成超分子结构。此配合物的热分解反应是分两步进行的,第一步反应的动力学方程为dαdT=Aφ.exp-E()R T3/2[(1-α)43(1-α)-13-]1-1,活化能E=151.8kJ/mol,指前因子lgA=16.9435;第二步反应的动力学方程为dαdT=Aφ.exp-E()R T32[(1-α)43(1-α)-13-]1-1,活化能E=201.5kJ/mol,指前因子lgA=7.5447。

The complex [Cu2 （phen）2（OH）2 （H2 O）2 ][Cu2 （phen）2 （OH）2 Cl2 ]Cl2· 6H2 O was synthesized in water solution and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. Be- sides, thermal decomposition kinetics of the complex was studied by thermal analysis technique. Experi- mental results showed that there were two-groups dinuclear coordination units in the complex, Cu2 （phen）2 （OH）2 （H2 O）2 is＋ and [Cu2 （phen）2 （OH）2Cl2 ], respectively. Copper atoms were all five-coordinated with distorted square pyramid geometry in the two coordination units. The supramolecular complex was assem- bled entirely through hydrogen bond. Thermal decomposition of the complex included two steps, the ki-netics of the first step wasda/dT=A/Ф·exp（-E/RT）3/2（1-a）^4/3[（1-a）^-1/3-1]^-1 , where E=151.8 kJ/mol, lgA= / 16. 9435 and the kinetic of the second step was da/dT=A/Ф·exp（-E/RT）3/2（1-a）^4/3[（1-a）^-1/3-1]^-1 , where E=201.5 kJ/mol, lgA=7. 5447.