Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.
Inorg Chem. 2010 Apr 5;49(7):3162-8. doi: 10.1021/ic901998p.
The thermal- and photoinduced valence tautomerism of a cobalt bis(dioxolene) complex is described. The thermal conversion is precipitous, complete within 10 K, and is accompanied by a 5 K hysteresis loop (107 K < T(1/2) < 112 K). Rapid thermal quenching (300 K --> 10 K in ca. 5 s) and photoinduced valence tautomerism result in trapping of the metastable Co(II)-state at low temperatures through intermolecular hydrogen bonding. This lattice stabilization results in unmatched kinetic and thermal stability for a valence tautomer from 10-50 K, with residual hs-Co(II) persisting until about 90 K.
本文描述了一个钴双二氧戊环配合物的热诱导和光诱导价态互变异构现象。热转换是急剧的，在 10 K 内完全完成，并且伴随着 5 K 的滞后环（107 K < T(1/2) < 112 K）。快速热淬火（300 K --> 10 K 在大约 5 s 内）和光诱导价态互变异构导致亚稳的 Co(II)-态通过分子间氢键在低温下被捕获。这种晶格稳定化导致价态互变异构在 10-50 K 之间具有无与伦比的动力学和热稳定性，残余的 hs-Co(II) 一直持续到约 90 K。
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