3,5-二氯水杨醛缩邻苯二胺铜配合物的合成、晶体结构及光谱学性质

Synthesis,Crystal Structure and Spectroscopic Property of [Cu(C_(20)H_(10)Cl_4O_2N_2)]·DMF

合成了3,5-二氯水杨醛缩邻苯二胺铜配合物[Cu(C20H10Cl4O2N2)]·DMF。通过元素分析、红外光谱、热重测试技术对其进行了表征,同时用X射线单晶衍射确定了其晶体结构;利用紫外-可见光吸收光谱、荧光激发和发射光谱研究了该配合物的光物理性能。结果表明,该晶体属于单斜晶系,空间群为P2(1)/n,a=0.81316(8)nm,b=1.53101(18)nm,c=1.87819(19)nm,β=92.4530(10)°,Z=4,最终偏差因子R1=0.0584,ωR2=0.1482,配合物的中心铜离子与席夫碱的2个O和2个N配位,形成1个五元环和2个六元环,从而构成了1个四配位的平面构型;配合物的热分解温度为384℃,具有很好的热稳定性;在DMF溶液体系中,配合物的荧光激发带位于360～480nm,荧光发射峰在507nm处,为蓝绿色荧光,最佳激发波长为440nm,禁带宽度2.59eV。

A Schiff base ligand,N,N＇-bis（3,5-dichlorosalicylaldehyde）-o-phenylenediamine,and its copper complex was synthesized.The compound was characterized by elemental analysis,FTIR,TG-DTG,single crystal X-ray diffraction,UV-Vis absorption spectroscopy,and fluorescence excitation and emission spectra.The high thermal decomposition temperature of 384 ℃ for the complex showed that it had high thermal stability.In its infrared spectrum,a strong band was observed at about 1616 cm-1.This band was due to the conjugated C N stretching vibration,and was shifted to higher frequency compared with the free ligand of 3,5-dichlorosalicylaldehyde and o-phenylenediamine.The new band at 530 cm-1 was assigned to Cu—O stretching vibration.The crystal of the copper（Ⅱ） complex belongs to monoclinic system with space group,P2（1）/n,a = 0.81316（8） nm,b = 1.53101（18） nm,c = 1.87819（19） nm,β = 92.4530（10） °,Z = 4,the final R1 = 0.058,and ωR2 = 0.148.The central copper ion of the complex coordinated with the two O and two N of the Schiff base to form a five-membered ring and two six-membered rings,which constituted a fourcoordinated planar conformation.The complex＇s UV absorption bands were at about 268,310 and 435 nm,where the absorption band at about 435 nm can be assigned to the intrinsic absorption of C N.Its fluorescence excitation is in the range of 360 ～ 480 nm,and its DMF solution emitted intensive blue-green fluorescence at the peak wavelength of 507 nm.Its optical gap was about 2.59 eV,which was determined by the intrinsic absorption band edge of the complex in DMF solution.