A tetranuclear Mn-diamond core complex as a functional mimic of both catechol oxidase and phenoxazinone synthase enzymes

Abstract

Through dioxygen activation, a tetranuclear Mn(II,III,III,II) diamond core, [Mn₄(HPTP*)₂(μ-O)₂(H₂O)₄](ClO₄)₄ (1) complex, has been synthesised using a suitably designed septadentate ligand framework (HPTP*H = 1,3-bis(bis((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amino)propan-2-ol). The newly prepared complex 1 was characterised using multiple spectroscopic techniques and X-ray crystallography. 1 exhibits excellent catalytic oxidation reactivity for the model substrates, namely, 3,5-di-tert-butylcatechol (3,5-DTBC) and 2-aminophenol, efficiently mimicking the enzymes catechol oxidase and phenoxazinone synthase, respectively. Remarkably, we employed aerial oxygen to catalyze the oxidation of these model substrates, 3,5-DTBC and 2-aminophenol, with turnover numbers of 835 and 14, respectively. A tetranuclear Mn-diamond core complex that mimics both catechol oxidase and phenoxazinone synthase could pave the way for further research into its potential as a multi-enzymatic functional mimic.