Magnetic bistability in a cobalt bis(dioxolene) complex: long-lived photoinduced valence tautomerism

Robert D Schmidt; David A Shultz; James D Martin

doi:10.1021/ic901998p

Magnetic bistability in a cobalt bis(dioxolene) complex: long-lived photoinduced valence tautomerism

Inorg Chem. 2010 Apr 5;49(7):3162-8. doi: 10.1021/ic901998p.

Authors

Robert D Schmidt¹, David A Shultz, James D Martin

Affiliation

¹ Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.

PMID: 20178340
DOI: 10.1021/ic901998p

Abstract

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.