Mono Versus Dinuclear Vanadium(V) Complexes: Solvent Dependent Structural Versatility and Electro Syntheses of Mixed-Valence Oxovanadium(IV/V) Entities in Solution

[Image: see text] Two mononuclear oxidovanadium(V) complexes type of [V(V)O(L(1))(OMe)(MeOH)] (1), [V(V)O(L(2))(OMe)(MeOH)] (2) and two [V(2)O(3)](4+) core of μ-oxidodioxidodivanadium(V) complexes (L(1))(O)V(V)–O–V(V)(O)(L(1)) (3) and (L(2))(O)V(V)–O–V(V)(O)(L(2)) (4) and two complexes [V(V)O(L(1))(8-Hq)] (5) and [V(V)O(L(2))(8-Hq)] (6) incorporating 8-hydroxyquinoline (8-hq) as co-ligand have been reported where L(1) [(E)-N′-(2-hydroxybenzylidene)cinnamohydrazide] and L(2) [(2E,N′E)-N′-(2-hydroxybenzylidene)-3-(naphthalen-1-yl)acrylohydrazide] are the dianionic forms of the conjugated keto-imine functionalized substituted hydrazone ligands. The μ-oxidodioxidodivanadium complexes are generated upon switching the solvent from methanol to acetonitrile. The X-ray analysis showed octahedral geometry for the mononuclear complexes 1, 2 and 5 but oxido-bridged dinuclear complexes 3 and 4 formed penta-coordinated square-pyramidal geometry about metal atoms. Two mixed-valence species of type II, 3a and 4a, of general formulae (L)(O)V(IV)–O–V(V)(O)(L), are being generated upon constant potential electrolysis (CPE) of 3 and 4 respectively. Frozen solution EPR spectra have 13 hyperfine lines, revealing the unpaired electron is majorly localized on one of the two vanadium centres. All these complexes have been well characterized by physio-chemical techniques and the density functional theory (DFT) calculations were applied to obtain further insight into the electronic structure of this type of molecule. The oxidomethoxido complexes 1 and 2 were taken to investigate the catechol oxidase mimicking activity following the oxidation of 3,5-di-tert-butyl catechol (3,5-DTBC) to 3,5-di-tert-butyl benzoquinone (3,5-DTBQ).