Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes. Issue 48 (11th October 2016)

• Record Type: Journal Article
• Authors: Li, Guo‐Ling; Kanegawa, Shinji; Yao, Zi‐Shuo; Su, Sheng‐Qun; Wu, Shu‐Qi; Huang, You‐Gui; Kang, Soonchul; Sato, Osamu
• Is Part Of: Chemistry. Volume 22:Issue 48(2016)
• Page Start: 17130
• Page End: 17135
• Publication Date: 2016-10-11
• Subjects: hysteretic transition -- intermolecular interactions -- magnetism -- polymorphism -- valence tautomerism; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603817
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 polymorph1A, 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 polymorph1B 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 of1B⋅ 2H2 O has a higher thermal relaxation temperature than that of1A⋅ 3H2 O. Abstract : Polymorphs : Two polymorphic structures (1A and1B ) have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs possess different arrangements of VT cations and exhibit distinct thermal‐ and photoswitched magnetic properties. Structure1B demonstrated a water‐tunable hysteretic transition (see figure).