物理化学学报 >> 2011, Vol. 27 >> Issue (07): 1587-1594.doi: 10.3866/PKU.WHXB20110705

热力学，动力学和结构化学 上一篇    下一篇

Mn(II)配合物的晶体结构及表面光电性能

金晶, 巩园园, 武汉清, 李雷, 牛淑云   

  1. 辽宁师范大学化学化工学院, 辽宁 大连 116029
  • 收稿日期:2011-03-03 修回日期:2011-05-04 发布日期:2011-06-28
  • 通讯作者: 牛淑云 E-mail:syniu@sohu.com
  • 基金资助:

    国家自然科学基金(20571037)和辽宁省创新团队项目(2007T092)资助

Crystal Structure and Surface Photoelectric Property of Mn(II) Coordination Complexes

JIN Jing, GONG Yuan-Yuan, WU Han-Qing, LI Lei, NIU Shu-Yun   

  1. School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China
  • Received:2011-03-03 Revised:2011-05-04 Published:2011-06-28
  • Contact: NIU Sun-Yun E-mail:syniu@sohu.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20571037) and Innovative Team Foundation of Educational Office of Liaoning Province, China (2007T092).

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摘要：

采用水热法合成3个新的Mn(II)配合物[Mn(SO4)(H2O)3]n (1), [Mn2.5(HPO4)(PO4)(H2O)2]n (2), [Mn(phen)2(H2O)2]·(C4H4O4)·4H2O (3) (phen=1,10-邻二氮杂菲). 用X射线单晶衍射、表面光电压光谱(SPS)、红外光谱(IR)、紫外-可见吸收光谱(UV-Vis)、电子顺磁共振谱(EPR)对配合物进行了表征. 结构解析表明: 配合物1是具有2D结构的配合物, 氢键将其连接成3D超分子; 配合物2是具有3D无限结构的配合物; 配合物3是单核配合物, 再由多种氢键连接, 形成3D超分子. SPS结果表明, 3个配合物在300-800 nm范围内都呈现明显的光伏响应, 表明它们均具有一定的光-电转换性能. 讨论了配合物结构, 空间维度和中心金属离子配位环境的不同对配合物表面光电性能的影响以及SPS与UV-Vis的关联: 配合物的结构维度越高、规则性越好, SPS响应强度越大; 中心金属离子的直接配位原子种类的不同、所处外晶场的强弱不同, SPS响应带的数目和位置明显不同.

关键词: Mn(II)配合物, 合成, 晶体结构, 氢键, 光电性能

Abstract:

Three Mn(II) complexes [Mn(SO4)(H2O)3]n (1), [Mn2.5(HPO4)(PO4)(H2O)2]n (2), [Mn(phen)2(H2O)2]?(C4H4O4)?4H2O (3) (phen=1,10-phenanthroline) were synthesized by a hydrothermal method and characterized by infrared spectrum (IR), ultraviolet-visible spectrum (UV-Vis), electron paramagnetic resonance spectrum (EPR), single crystal X-ray diffraction and surface photovoltage spectrum (SPS). The structural analyses indicate that complex 1 is a 2D coordination polymer and hydrogen bonds link the polymer to a 3D infinite structure. Complex 2 is a 3D coordination polymer. Complex 3 is a mononuclear complex and diverse hydrogen bonds connect the complex to the 3D supramolecule. SPS results indicate that the three complexes exhibit obvious surface photovoltage responses between 300-800 nm, which reveals that they possess a definite photoelectric conversion property. The structure of the complex, its dimensions and the coordination environment of the central metal affect obviously SPS: the intensity of the surface photovoltage (SPV) response bands become larger with increasing of dimensions and regularity of structure; differences in the species of direct coordination atoms and the strength of the crystal field around the central metal ions lead to the change of number and position of the response bands. Additionally, the association between SPS and UV-Vis were discussed.

Key words: Mn(II) complex, Synthesis, Crystal structure, Hydrogen bond, Photoelectric property