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- Title
Effect of Intermolecular Interactions on Metal‐to‐Metal Charge Transfer: A Combined Experimental and Theoretical Investigation.
- Authors
Jiao, Cheng‐Qi; Meng, Yin‐Shan; Yu, Yang; Jiang, Wen‐Jing; Wen, Wen; Oshio, Hiroki; Luo, Yi; Duan, Chun‐Ying; Liu, Tao
- 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 π⋅⋅⋅π 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.
- Subjects
INTERMOLECULAR interactions; CHARGE transfer; COUNTER-ions; ANIONS; LIGANDS (Chemistry); COBALT
- Publication
Angewandte Chemie, 2019, Vol 131, Issue 47, p17165
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201909495