Chinese-Lantern shaped [MnII2MnIII6NaI3] cluster assembled from Schiff base and azide bridges : synthesis, magnetic study and catecholase-like activity

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Chattopadhyay, Krishna and Dutta, Biswarup and Dutta, Shyamali and Manna, Anupama and Craig, Gavin A. and Mandal, Manas and Murrie, Mark and Ray, Debashis (2024) Chinese-Lantern shaped [MnII2MnIII6NaI3] cluster assembled from Schiff base and azide bridges : synthesis, magnetic study and catecholase-like activity. Inorganica Chimica Acta, 572. 122270. ISSN 0020-1693 (https://doi.org/10.1016/j.ica.2024.122270)

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Abstract

A multisite Schiff base, H2damp, derived from the condensation of o-vanillin and a sterically constrained amino-alcohol (2-amino-2-methylpropan-1-ol) was utilized to isolate a new mixed valence heterometallic complex [Na3MnIII6MnII2(damp)6(µ4-O)2(µ1,3-O2CCH3)2(µ1,1-N3)6(µ1,1,3-N3)(H2O)2]·5H2O·CH3OH (1). Room temperature reaction of H2damp in MeOH with Mn(II) acetate and NaN3 provided the complex having MnII2MnIII6NaI3 core. X-ray structure determination revealed the use of azide ancillary ligands for the growth of the complex on ligand-bound MnIII3O fragments. The variable temperature magnetic characterization of 1 revealed intramolecular anti-ferromagnetic exchange interactions. Complex 1 also showed catalytic property for the aerial oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) with a turnover number (kcat) of 392 h−1. EPR and mass spectrometric analysis established the probable mechanism of catalytic oxidase reactivity on the model substrate. In EPR study the characteristic peak at g ∼ 2 allowed us to spot the presence of an organic radical confirming the conversion of DTBCH2 to DTBQ in radical pathway.

ORCID iDs

Chattopadhyay, Krishna, Dutta, Biswarup, Dutta, Shyamali, Manna, Anupama, Craig, Gavin A. ORCID logoORCID: https://orcid.org/0000-0003-3542-4850, Mandal, Manas, Murrie, Mark and Ray, Debashis;
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