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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (18): 2108-2116. 上一篇    下一篇

研究论文

系列Ni(II)配位超分子的合成、结构及表面光电性能

金晶1，李丹1，李雷1，史忠丰1，刘东伟1，牛淑云*,1，张广宁2   

  1. (1辽宁师范大学化学化工学院 大连 116029)
    (2辽宁师范大学功能材料化学研究所 大连 116029)
  • 投稿日期:2011-03-05 修回日期:2011-04-15 发布日期:2011-05-17
  • 通讯作者: 牛淑云 E-mail:syniu@sohu.com
  • 基金资助:

    国家自然科学基金;辽宁省教育厅创新团队资助项目

Syntheses, Structures and Surface Photo-electric Properties of A Series of Ni(II) Coordination Supramolecules

Jin Jing1 Li Dan1 Li Lei1 Shi Zhongfeng1 Liu Dongwei1 Niu Shuyun*,1 Zhang Guangning2   

  1. (1 School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029)
    (2 Institute of Chemistry for Functionalized Materials of Liaoning Normal University, Dalian 116029)
  • Received:2011-03-05 Revised:2011-04-15 Published:2011-05-17

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以不同的刚性有机羧酸衍生物为配体, 采用水热方法合成了4个Ni(II)的配位超分子化合物, {[Ni(bipy)(H2O)4]•(bdc)} (1), [Ni(PhCOO)(phen)(H2O)3]•(PhCOO) (2), [Ni(dcpz)(H2O)4] (3), [Ni(pic)2(H2O)2] (4) (H2bdc＝间苯二甲酸, PhCOO＝苯甲酸根, phen＝1,10-邻菲咯啉, H2dcpz＝吡唑-3,5-二羧酸, Hpic＝吡嗪-2-甲酸, bipy＝2,2-联吡啶). 通过单晶X射线衍射、XRD、表面光电压光谱(SPS)、IR和UV-Vis吸收光谱等方法对化合物进行了表征. 结构解析表明, 化合物(1)～(4)均为单核配合物, 再通过分子间氢键连成具有1D, 2D或3D氢键网络结构. 重点是对比研究了配合物的SPS. 4个配合物的SPS在300～800 nm范围内都呈现正的光伏响应, 表明它们均具有一定的光电转换能力. 讨论了配合物的结构、有机配体种类、氢键及中心金属离子的配位微环境对其表面光电性能的影响, 并将SPS与UV-Vis吸收光谱进行了关联.

关键词: Ni(II)配位超分子, 合成, 结构, 氢键, 光电性能

Four Ni (II) coordination supramolecules {[Ni(bipy)(H2O)4]•(bdc)} (1), [Ni(PhCOO)(phen)- (H2O)3]•(PhCOO) (2), [Ni(dcpz)(H2O)4] (3), [Ni(pic)2(H2O)2] (4) were hydrothermally synthesized with the derivatives of different rigid organic carboxylic acid as ligands (H2bdc＝m-phthalic acid, PhCOO＝benzoate, H2dcpz＝pyrazole-3,5-dicarboxylic acid, Hpic＝2-pyrazinecarboxylic acid, bipy＝2,2- bipyridine, phen＝1,10-phenanthroline). The crystal structures of the complexes were determined by X-ray single crystal diffraction, and complexes were characterized by surface photovoltage spectrum (SPS), IR, UV-Vis-NIR spectra and XRD. The results indicate that complexes (1)～(4) are mononuclear complexes, connected by intermolecular hydrogen bonds into 1D, 2D or 3D hydrogen-bonded network structure. Comparative study of SPS for four complexes shows that they all exhibit positive surface photovoltage response (SPV) in the range of 300～800 nm, which indicates that they all possess certain photo-electric conversion properties. The effect of structure of the complexes, type of organic ligands, hydrogen bonds and coordination environment of the central metal ions on the photo-electric properties were discussed. Furthermore, the SPS and UV-Vis spectra were interrelated.

Key words: Ni(II) coordination supramolecule, synthesis, structure, hydrogen bond, photo-electric property

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