Ligand centered radical pathway in catechol oxidase activity with a trinuclear zinc-based model: Synthesis, structural characterization and luminescence properties

•Synthesis and characterization of a zinc(II)–Schiff base complex.•Both ligand and complex show good fluorescence properties in solution.•The zinc complex mimics catecholase significantly.•Ligand centered radical mechanistically catalyzes the reaction.

A new trinuclear zinc(II) complex, [Zn3(L)(NCS)2](NO3)2·CH3OH·H2O (1), of a (N,O)-donor compartmental Schiff base ligand (H2L = N,N′-bis(3-methoxysalicylidene)-1,3-diamino-2-propanol), has been synthesized in crystalline phase. The zinc(II) complex has been characterized by elemental analysis, IR spectroscopy, UV–Vis spectroscopy, powder X-ray diffraction study (PXRD), 1H NMR, EI mass spectrometry and thermogravimetric analysis. PXRD revealed that 1 crystallizes in P − 1 space group with a = 9.218 Å, b = 10.849 Å, c = 18.339 Å, with unit cell volume is 2179.713 (Å)3. Fluorescence spectra in methanolic solution reflect that intensity of emission for 1 is much higher compared to H2L and both the compounds exhibit good fluorescence properties. The complex 1 exhibits significant catalytic activities of biological relevance, viz. catechol oxidase. In methanol, it efficiently catalyzes the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to corresponding quinone via formation of a dinuclear species as [Zn2(L)(3,5-DTBC)]. Electron Paramagnetic Resonance (EPR) experiment suggests generation of radicals in the presence of 3,5-DTBC and it may be proposed that the radical pathway is probably responsible for conversion of 3,5-DTBC to 3,5-DTBQ promoted by complex of redox-innocent Zn(II) ion.

Graphical abstractA trinuclear zinc(II)–Schiff base complex has been employed to mimic catechol oxidase activity. This zinc–Schiff base complex exhibits significant catechol oxidation in methanol through ligand centered pathway, which is the rare example among the redox innocent zinc complexes till date.Figure optionsDownload full-size imageDownload as PowerPoint slide