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Transition from a Metal‐Localized Mixed‐Valence Compound to a Fully Delocalized and Bridge‐Biased Electrophore in a Ruthenium–Amine–Ruthenium Tricenter System
Author(s) -
Tang JianHong,
Shao JiangYang,
He YanQin,
Wu SiHai,
Yao Jiannian,
Zhong YuWu
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601806
Subject(s) - ruthenium , delocalized electron , substituent , valence (chemistry) , amine gas treating , chemistry , density functional theory , photochemistry , transition metal , metal k edge , electron paramagnetic resonance , electrochemistry , computational chemistry , stereochemistry , catalysis , organic chemistry , nuclear magnetic resonance , electrode , physics
A series of cyclometalated diruthenium complexes with a redox‐active amine bridge were synthesized. Depending on the terminal ligands of the ruthenium components and the substituent on the amine unit, the one‐electron‐oxidized state can be either in the form of a weakly or strongly coupled mixed‐valence diruthenium complex, a fully charge‐delocalized three‐center system, or a bridge‐biased electrophore. This transition among different electronic forms was supported by electrochemistry, near‐infrared absorption, electron paramagnetic resonance, and density functional theory analysis.