Double dicyanamide decorated double phenoxide bridged MnIII dimer with single-molecule magnetic behaviour and bio-catalytic activity

Abstract

Herein, we report the magnetic properties and bio-catalytic activity of a flying bee-like double phenoxido bridged dinuclear MnIII-Schiff base complex decorated with double dicyanamide (dca−) ligands and formulated as: [Mn2(L)2(dca)2] (1) (where H2L = 2,2′-((1E,1′E)-(ethane-1,2-diylbis(azanylylidene))-bis(ethan-1-yl-ylidene))diphenol). The complex has been synthesised by one-pot stepwise reaction of the tetradentate Schiff’s base ligand H2L with MnCl2 and dca− at 1:1:2 ratio under aerobic conditions. It has been characterized by single crystal X-ray diffraction (SC-XRD) and spectroscopic techniques. Complex 1 contains two MnIII ions connected by a double phenoxido bridge in an octahedral geometry and terminal dca− ligands. The dimers are connected to other dimers through both hydrogen bonding and π-interactions to form an extended supramolecular network. The present study reveals that in presence of tetradentate Schiff base ligands, the use of a 1:2 Mn:dca− ratio leads to formation of a dimeric MnIII complex in contrast to the discrete mononuclear complexes or 1D structures previously obtained for the Mn:dca− ratio of 1:1. The magnetic study indicates that the dimeric MnIII complex shows a negligible MnIII–MnIII interaction and a large anisotropy. The AC susceptibility measurements indicate that complex 1 behaves as a field-induced single-molecule magnet (SMM), with a high energy barrier of 73(4)K. The study of model catechol oxidase-like enzyme activity of complex 1 indicates that the dimeric MnIII complex acts as an active catalyst (kcat = 34.94 h−1) in the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) in presence of aerial O2 in acetonitrile medium.