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Indexed by:Journal Papers

Date of Publication:2019-11-18

Journal:ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

Included Journals:PubMed、SCIE

Volume:58

Issue:47

Page Number:17009-17015

ISSN No.:1433-7851

Key Words:cobalt; metal-to-metal charge transfer; spin transition; thermochromics; pi center dot center dot center dot pi interactions

Abstract:Understanding the effects of intermolecular interactions on metal-to-metal charge transfer (MMCT) is crucial to develop molecular devices by grafting MMCT-based molecular arrays. Herein, we report a series of solvent-free {Fe2Co2} compounds sharing the same cationic tetranuclear {[Fe(PzTp)(CN)(3)](2)[Co(dpq)(2)](2)}(2+) (PzTp(-)=tetrakis(pyrazolyl)borate, dpq=dipyrido[3,2-d:2',3'-f]quinoxaline) square units but having anions with different size, including BF4-, PF6-, OTf-, and [Fe(PzTp)(CN)(3)](-). Intermolecular pi center dot center dot center dot pi interactions between dpq ligands, which coordinate to cobalt ions in the {[Fe(PzTp)(CN)(3)](2)[Co(dpq)(2)](2)}(2+) units, can be modulated by introducing different counterions, regulating the distortion of the CoN6 octahedron and ligand field around the cobalt ions. This change results in different MMCT behavior. Computational analyzes reveal the substantial role of the intermolecular interactions tuned by the presence of different counteranions on the MMCT behavior.