Spin‐State‐Switching Rearrangements of Bis(dioxolene)‐Bridged CrCo Complexes: A DFT Study

Density functional theory calculations (UTPSSh/6‐311++G(d,p)) of electronic structure, energy characteristics and magnetic properties of a series of heterometallic CrCo complexes comprising redox‐active bis(dioxolene) bridging ligands (3,3,3’,3’‐tetramethyl‐5,6,5’,6’‐tetrahydroxy‐1,1’‐spiro‐bis(indan) and 2,3,6,7‐tetrahydroxy‐9,10‐dimethyl‐9,10‐dihydro‐9,10‐ethanoanthracene) and ancillary tetradentate nitrogen‐containing bases (tris(2‐pyridylmethyl)amine and N,N′‐dialkyl‐2,11‐diaza[3.3]‐(2,6)pyridinophane derivatives) were performed. The compounds prone to manifest spin‐state switching rearrangements involving cobalt centre have been revealed. Analysis of the results obtained and their comparison with those found previously open wide prospects for the purposeful search for a broad variety of new magnetically bistable heterometallic dinuclear paramagnetic species with a prospect of useful application in the design of smart dynamic materials. Among a series of computationally investigated CrCo dinuclear compounds with redox‐active bridging bis(dioxolenes) and ancillary tetradentate N‐donor bases, the complexes prone to manifest spin‐crossover or valence tautomerism have been revealed. Data obtained open possibilities for the targeted design of new systems – building blocks for molecular electronics devices.