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

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

ZHENG Ji ^1, ,
XING Li-Rui ² ,
LI Dan 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 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).

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.
- Cuprophilicity,
- Frontal packing,
- Phosphorescent emissive state,
- Halogen bond,
- Reduced density gradient,
- Quantum theory of atoms in molecules
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