Computational insight into magnetic behaviour of cobalt tris(2-pyridylmethyl)amine complexes with dioxolenes incorporating stable radicals

Abstract

A computational DFT UTPSSh/6–311++G(d,p) modelling of a series of cobalt complexes with tris(2-pyridylmethyl)amine derivatives and dioxolenes functionalized with nitronylnitroxide or 1,2,3,5-dithiadiazolyl moieties was performed. The possibility of the occurrence of magnetic bistability mechanisms was predicted. The dependence of character and strength of the exchange interactions between the paramagnetic centres on the nature of radical group and way of attachment of the latter (directly or via phenylene linker) was revealed. The comparison of the results obtained with those found for analogous compounds non-comprising radical substituents allows one to plan the directional synthesis of new paramagnetic species undergoing spin-state switching rearrangements.