物理化学学报 >> 2017, Vol. 33 >> Issue (11): 2133-2140.doi: 10.3866/PKU.WHXB201706051

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极长与极短的铜铜距离-吡唑环三核亚铜配合物亲铜作用本质及发光调控

郑霁1,邢立锐2,李丹1,*()   

  1. 1 暨南大学化学与材料学院,广州510632
    2 汕头大学化学系,广东汕头515063
  • 收稿日期:2017-04-26 发布日期:2017-08-25
  • 通讯作者: 李丹 E-mail:danli@jnu.edu.cn
  • 基金资助:
    国家重点基础研究发展计划(973)(2012CB821706);国家重点基础研究发展计划(973)(2013CB834803);国家自然科学基金(91222202);国家自然科学基金(21171114)

Extreme Long and Extreme Short Cu-Cu Distances:Nature of Cuprophilicity and Luminescence Modification in Cu (Ⅰ)-based Cyclic Trinuclear Complexes

Ji ZHENG1,Li-Rui XING2,Dan LI1,*()   

  1. 1 College of Chemistry and Materials Science, Jinan University, Guangzhou 510632 P. R. China
    2 Department of Chemistry, Shantou University, Shantou 515063, Guangdong Province P. R. China
  • Received:2017-04-26 Published:2017-08-25
  • Contact: Dan LI E-mail:danli@jnu.edu.cn
  • Supported by:
    The project was supported by the National Key Basic Research Program of China (973)(2012CB821706);The project was supported by the National Key Basic Research Program of China (973)(2013CB834803);National Natural Science Foundation of China(91222202);National Natural Science Foundation of China(21171114)

摘要:

本文结合近年来亲金属作用研究领域的进展,针对本课题组在环三核亚铜配合物方面的最新研究成果,讨论了两个铜(Ⅰ)-铜(Ⅰ)作用相差悬殊的体系。一是通过构筑具有环三核单元的三棱柱笼状配合物,确认在正堆积模式下即使环三核单元之间亲铜作用极弱依然可以在磷光发射态中产生强亲铜作用,且通过配体的预留配位点与Cu2I2簇连结从而得到自校准大范围发光温度计;二是通过与亲铜作用正交的Br-Br卤键,实现环三核亚铜配合物前所未有的极短铜(Ⅰ)-铜(Ⅰ)距离,通过各种电子结构分析方法研究其本质。结果表明即使当铜(Ⅰ)-铜(Ⅰ)距离很接近铜的范德华半径和时,其本质依然为闭壳层作用,而Br-Br作用总为闭壳层作用,且该体系中最强的Br-Br作用很好地体现出一个Br原子的σ穴和另一个Br原子的负静电势区域的匹配性。

关键词: 亲铜作用, 正堆积, 磷光发射态, 卤键, 约化密度梯度, 分子中的原子的量子理论

Abstract:

This monograph focuses on recent progress in the research field of metallophilicity, in combination of our latest results on Cu(Ⅰ)-based cyclic trinuclear complexes, mainly discussing two examples with very different cuprophilicity. One is by constructing triangular coordination prisms bearing cyclic trinuclear units, confirming that strong cuprophilic attraction could exist in the phosphorescent emissive state under frontal packing mode even when the cuprophilicity is extreme weak at ground state, and by coordination with a Cu2I2 cluster with an additional coordinate site in the ligand, so that a self-calibrated wide-range luminescent molecular thermometer was obtained. The other is the realization of the shortest Cu-Cu distance so far in this field by Br-Br halogen bond orthogonal to cuprophilicity, followed by the investigation using several kinds of electronic structure analysis. The result shows that even when the Cu-Cu distance approaches the van der Waals radii sum of Cu, its nature is still closed-shell interaction, which is also the nature of all Br-Br interaction, and the strongest Br-Br interaction in this system displays good matching between the σ-hole of a Br atom and the belt of negative potential of another Br atom.

Key words: Cuprophilicity, Frontal packing, Phosphorescent emissive state, Halogen bond, Reduced density gradient, Quantum theory of atoms in molecules

MSC2000: 

  • O641