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Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes
Author(s) -
Li GuoLing,
Kanegawa Shinji,
Yao ZiShuo,
Su ShengQun,
Wu ShuQi,
Huang YouGui,
Kang Soonchul,
Sato Osamu
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.201603817
Subject(s) - intermolecular force , valence (chemistry) , tautomer , cobalt , thermal hysteresis , crystallography , chemistry , polymorphism (computer science) , thermal , chemical physics , stereochemistry , phase transition , molecule , condensed matter physics , thermodynamics , inorganic chemistry , organic chemistry , physics , biochemistry , genotype , gene
Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π ⋅⋅⋅ π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π ⋅⋅⋅ π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B⋅ 2H 2 O has a higher thermal relaxation temperature than that of 1A⋅ 3H 2 O.