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

引用本文: 郑霁, 邢立锐, 李丹. 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[J]. 物理化学学报, 2017, 33(11): 2133-2140. doi: 10.3866/PKU.WHXB201706051 shu

Citation: ZHENG Ji, XING Li-Rui, LI Dan. Extreme Long and Extreme Short Cu-Cu Distances:Nature of Cuprophilicity and Luminescence Modification in Cu (I)-based Cyclic Trinuclear Complexes[J]. Acta Physico-Chimica Sinica, 2017, 33(11): 2133-2140. doi: 10.3866/PKU.WHXB201706051 shu

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.
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
基金项目:
国家重点基础研究发展计划（973）（2012CB821706，2013CB834803）和国家自然科学基金（91222202，21171114）资助项目

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:

English

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

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 Date: 26 April 2017
Revised Date: 26 May 2017
Fund Project:
The project was supported by the National Key Basic Research Program of China (973)(2012CB821706,2013CB834803),the National Natural Science Foundation of China (91222202,21171114).

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:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

English

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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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