高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (10): 2161.doi: 10.7503/cjcu20180076

• 研究论文:无机化学 • 上一篇    下一篇

由芳香羧酸构筑的系列Ni(Ⅱ)配合物的合成、 结构及光电性能

贠吉星, 胡志莉, 李禹蒙, 金晶(), 陈冲, 鄢欣, 刘永华, 丁榆, 迟玉贤(), 牛淑云   

  1. 辽宁师范大学化学化工学院, 大连 116029
  • 收稿日期:2018-01-25 出版日期:2018-09-29 发布日期:2018-09-29
  • 作者简介:

    联系人简介: 金 晶, 女, 博士, 副教授, 主要从事功能配合物方面的研究. E-mail: jinjing_crystal@126.com;迟玉贤, 女, 博士, 副教授, 主要从事发光配合物方面的研究. E-mail: yxchi@lnna.edu.cn

  • 基金资助:
    国家自然科学基金(批准号:21133005)、 辽宁省自然科学基金(批准号:20170540576)和辽宁省教育厅基金(批准号: L201783635)资助.

Synthesis, Structure and Photoelectric Property of A Series of Ni(Ⅱ) Complexes Constructed Through Aromatic Carboxylic Ligands

YUN Jixing, HU Zhili, LI Yumeng, JIN Jing*(), CHEN Chong, YAN Xin, LIU Yonghua, DING Yu, CHI Yuxian*(), NIU Shuyun   

  1. School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China
  • Received:2018-01-25 Online:2018-09-29 Published:2018-09-29
  • Contact: JIN Jing,CHI Yuxian E-mail:jinjing_crystal@126.com;yxchi@lnna.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21133005), the Natural Science Foundation of Liaoning Province, China(No.20170540576) and the Educational Foundation of Liaoning Province, China(No.L201783635).

摘要:

采用水热法设计合成了6个基于芳香羧酸的Ni(Ⅱ)配合物: [Ni(pz)4(H2O)2]·2H2btc·H2O(1), {[Ni2(pz)8(btec)]·4H2O}n(2), {[Ni(H2btec)(phen)]∙2H2O}n(3), [Ni(Hbdc)2(pz)4](4), {[Ni3(bdc)3(pz)12]·2H2O}n(5)和[Ni(bdc)(pz)2(H2O)]n(6)(pz=吡唑, H3btc=1,3,5-苯三甲酸, H4btec=1,2,4,5-苯四甲酸, phen=1,10-邻菲罗啉, H2bdc=邻苯二甲酸). 通过单晶X射线衍射、 红外光谱(IR)、 紫外-可见-近红外吸收光谱、 元素分析、 粉末X射线衍射(XRD)和表面光电压光谱(SPS)对其进行了结构和性质表征. 6个配合物的金属Ni(Ⅱ)中心呈五或六配位. 配合物1和4具有完全由氢键网联成的2D超分子结构; 配合物2和3是通过采取单齿/桥双齿配位模式的btec4-构筑的2D配位骨架结构; 配合物5和6是由采取单齿/螯合双齿配位模式的bdc2-构筑的1D配位骨架结构, 并由氢键连接成2D结构. 6个配合物在紫外和可见光诱导下均呈现出一定的光-电转换性能. 当对配合物施加外加电场时, 6个配合物的光电响应因配合物组成、 结构键连方式以及配体种类的不同而呈现规律性变化.

关键词: 芳香羧酸, Ni(Ⅱ)配合物;, 晶体结构, 光物理性质, 光电性能

Abstract:

Six Ni(Ⅱ) complexes based on aromatic carboxylic ligands, [Ni(pz)4(H2O)2]·2H2btc·H2O(1), {[Ni2(pz)8(btec)]·4H2O}n(2), {[Ni(H2btec)(phen)]∙2H2O}n(3), [Ni(Hbdc)2(pz)4](4), {[Ni3(bdc)(pz)12]·2H2O}n(5) and [Ni(bdc)(pz)2(H2O)]n(6)(pz=pyrazole, H3btc=1,3,5-benzenetricarbolylic acid, H4btec=1,2,4,5-benzenetetracarboxylic acid, phen=1,10-phennanthroline, H2bdc=1,2-benzenedicarboxylic acid), were hydrothermally synthesized. All the complexes were structurally and photophysically characterized by means of single crystal X-ray diffraction, infrared(IR) and UV-Vis-NIR electronic spectra, elemental analysis, X-ray diffraction(XRD) and surface photovoltage spectra(SPS). The Ni(Ⅱ) centers in six complexes have the square-pyramid or octahedral coordination environment. Complexes 1 and 4 have 2D supramolecular structure networked by hydrogen bonds. Complexes 2 and 3 possess 2D coordination framework structure constructed by btec4- ligands with monodentate and monoatomic bridging modes. Complexes 5 and 6 have 1D coordination chain structure built by bdc2- anions with monodentate/chelating coordination modes, which are further networked into 2D supramolecules by hydrogen bonds. All the six complexes exhibit certain photo-electric conversion properties under the inducement of UV-Vis lights. When a positive electric field is applied to the six complexes, the intensity change of photoelectric response of the six complexes presents difference which correlates with the bonding mode of the structure and type of the organic ligands.

Key words: Aromatic carboxylic acid, Ni(Ⅱ) complex;, Crystal structure, Photophysical property, Photoelectric property

中图分类号: 

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