【摘要】 采用水热法合成了2种新型超分子配合物[Cu(C6H4O2N)2(H2O)4](1)和[Cd(C6H4O2N)2(H2O)4](2),通过元素分析、红外光谱、热分析、X-射线衍射等技术对其进行了表征.2种配合物均属三斜晶系,空间群P1,配合物1晶胞参数a=0.7769(2)nm,b=0.9186(2)nm,c=1.0725(3)nm,α=92.905(4)°,β=95.024(4)°,γ=111.117(3)°,V=0.7085(3)nm3,Z=2,Mr=379.81,Dc=1.780 g/cm3,F(000)=390,μ=1.589 mm-1,最终偏离因子R1=0.022 4,R2=0.067 5;配合物2晶胞参数a=0.643 94(12)nm,b=0.695 98(13)nm,c=0.941 53(18)nm,α=94.878(3)°,β=104.733(3)°,γ=111.986(2)°,V=0.370 69(12)nm3,Z=1,Mr=428.67,Dc=1.920 g/cm3,F(000)=214,μ=1.518 mm-1,最终偏离因子R1=0.027 3,R2=0.074 6.配合物的中心原子M2+(M2+=Cu2+,Cd2+)与2个吡啶-4-甲酸根及4个H2O配位,形成具有畸变八面体构型的基本结构单元,相邻单元通过O—H…O氢键的相连拓展为三维超分子体系.在实验的基础上,采用密度泛函理论(DFT)的B3LYP/Lanl2dz计算方法对2种配合物进行了几何优化、前线轨道能量、单点能量等后续计算.更多还原

【Abstract】 Two compounds [Cu(C6H4O2N)2(H2O)4](1),[Cd(C6H4O2N)2(H2O)4](2) were synthesized through hydrothermal method.The structure was characterized by elemental analysis,IR spectroscopy,thermal analysis and single-crystal X-ray diffraction.Two complexes crystallize in triclinic system,space group P1.Crystal data of 1:a=0.7769(2)nm,b=0.9186(2)nm,c=1.0725(3)nm,α=92.905(4)°,β=95.024(4)°,γ=111.117(3)°,V=0.7085(3)nm3,Z=2,Mr=379.81,Dc=1.780g/cm3,F(000)=390,μ=1.589mm-1,the final R1 and R2 are 0.0224 and 0.0675.Crystal data of 2:a=0.64394(12)nm,b=0.69598(13)nm,c=0.94153(18)nm,α=94.878(3)°,β=104.733(3)°,γ=111.986(2)°,V=0.37069(12)nm3,Z=1,Mr=428.67,Dc=1.920g/cm3,F(000)=214,μ=1.518mm-1,the final R1 and R2 are 0.0273 and 0.0746.The central Cu2+,Cd2+ ion of two compounds were in slightly distorted octahedron geometry completed by two nitrogen atoms from two 4-Pyridinecarboxylic acid radical and four oxygen atoms from four coordinated water molecules.Through the O—H…O hydrogen bonds,the neighboring units were linked into a two-dimensional planar structure,which were further organized by different intermolecular hydrogen bonds(O—H…O) to afford a 3D supramolecular structure.On the basis of the experimentation,the structure of two complexes were optimized by using DFT(B3LYP/Lanl2dz) methods,and the energies of frontier molecular orbitals and zero-point energies of the molecule were calculated and discussed.更多还原