应用化学 ›› 2010, Vol. 27 ›› Issue (11): 1334-1338.DOI: 10.3724/SP.J.1095.2010.00034

• 研究论文 • 上一篇    下一篇

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

张晓松,丁国华*,齐巧珍   

  1. (桂林理工大学化学与生物工程学院 桂林 541004)
  • 收稿日期:2010-01-14 修回日期:2010-04-13 出版日期:2010-11-10 发布日期:2010-11-10
  • 通讯作者: 丁国华,男,副教授; E-mail:dinggh@glite.edu.cn; 研究方向:有机功能材料
  • 基金资助:
    广西科学研究与技术开发计划项目(桂科能0842003-38),广西教育厅科研项目(067003)

Synthesis, Crystal Structure and Spectroscopic Property of [Cu(C20H10Cl4O2N2)]·DMF

ZHANG Xiao-Song, DING Guo-Hua*, QI Qiao-Zhen   

  1. (College of Chemistry and Biological Engineering,Guilin University of Technology,Guilin 541004)
  • Received:2010-01-14 Revised:2010-04-13 Published:2010-11-10 Online:2010-11-10

摘要:

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360~480 nm,荧光发射峰在507 nm处,为蓝绿色荧光,最佳激发波长为440 nm,禁带宽度2.59 eV。

关键词: 二氯水杨醛, 铜(II)配合物, 晶体结构, 光谱特性

Abstract:

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 fourcoordinated 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.

Key words: dichlorosalicylaldehyde, copper(II) complex, crystal, spectral characteristics

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