Bidirectional photoswitching of magnetic properties at room temperature: ligand-driven light-induced valence tautomerism† †Electronic supplementary information (ESI) available: Derivation of the non-linear regression fitting functions, crystallographic details, magnetization and electrochemical data, EPR and electronic absorption spectra. CCDC 1015850–1015852 and 1058866. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00130g

Valence tautomeric (VT) metal complexes are highly promising bistable molecular compounds for applications as molecular switches in molecular electronics and spintronics. Although VT species can be switched with light, the photoswitching in all reported systems requires very low temperatures (usually below 20 K) because photoinduced states are highly unstable at room temperature. The thermal instability hinders any practical application of these complexes in genuine devices. In this report, for the first time we demonstrate photoswitching of VT species and associated magnetic properties at room temperature. The bidirectional photoswitching in solution is due to cis–trans photoisomerizable 4-styrylpyridine ligands deliberately integrated into cobalt dioxolene molecular complexes. The novel type of photoswitching has been coined Ligand-Driven Light-Induced Valence Tautomerism (LD-LIVT). The photoconversion of VT states of 28% has been achieved in solution at room temperature. The photoinduced states show extraordinary thermal stability for hours at room temperature, as compared to common nanoseconds reported previously. The switching proceeds at molecular level with the effective photoswitching rate of 3 10 molecules per s under our conditions. Consequently, this work may open new horizons in applications of molecular switches based on VT metal complexes in molecular devices functioning at room temperature.