Solution and solid-state light-induced transformations in heterometallic vanadium-ruthenium nitrosyl complex

The work is devoted to the preparation and photochemical investigations of novel binuclear heterometallic complex [Ru(NO)(NO2)2(μ-NO2)(μ−CH3COO)(μ-O)VO(dbbpy)]·CH3CN (dbbpy - 4,4′-di-tert-butyl-2,2′-bipyridyl), which obtained with quantitative yield. structure determined by single crystal X-ray diffraction DFT calculations. On one hand, irradiation at 445 nm an acetonitrile solution leads a NO photo-release reaction. light excitation induces charge transfer from NO2 dbbpy ligands antibonding orbitals ON-Ru-O-V chain, leading release, confirmed DFT. quantum yield Ru-NO photo-cleavage 0.57 ± 0.05 %. products photolysis (NO paramagnetic RuIII complex) are Griess test EPR-spectroscopy. other in solid phase 10 K results formation metastable bond isomer Ru-ON (MS1), detected infrared spectroscopy. stretching vibration ν(NO) band MS1 (1750 cm−1) shifted 150 cm−1 lower energy respect ground state GS (1900 cm−1). population about 5%. thermally decays 120−140 back GS. Hence, this represents bifunctional platform, can release nitric oxide reversibly switch ligand coordination state. It shown, that presence vanadium strongly influences properties ruthenium nitrosyl both solution.