Issue 26, 2015

Anion coordination selective [Mn3] and [Mn4] assemblies: synthesis, structural diversity, magnetic properties and catechol oxidase activity

Abstract

Syntheses, crystal structures, magnetic properties and catechol oxidation behavior are presented for [Mn3] and [Mn4] aggregates, [MnIII2MnII(O2CMe)4(dmp)2(H2O)2]·2H2O (1·2H2O), [MnIII2MnII(O2CCH2Cl)4(dmp)2(H2O)2]·H2O·MeOH (2·H2O·MeOH), [MnIII43-O)(dmp)4(μ-DMSO)(N3)(DMSO)(H2O)]ClO4·DMSO (3·ClO4·DMSO), and [MnIII43-O)(dmp)4(μ-DMSO)(ClO4)(DMSO)(H2O)]ClO4·DMSO (4·ClO4·DMSO), developed with single type ligand H2dmp, 2-[(2-hydroxy-1,1-dimethyl-ethylimino)-methyl]-phenol. The successful isolation of 1–4 resulted from a systematic exploration of the effect of MnII salts, added carboxylates, Mn/H2dmp ratio, presence of azide, and other reaction conditions. The cores of 1 and 2 are similar and consist of a linear MnIIIMnIIMnIII unit in a carboxylate and H2dmp environment, revealing a central MnII ion in a different environment and terminal MnIII ions available for the introduction of structural and magnetic anisotropy to the system. The cores of 3 and 4 are also similar and consist of a distorted incomplete-adamantane type Mn4 coordination assembly in a carboxylate-free environment built on a triangular [MnIII33-O)] unit. The magnetic behavior of complexes 1–3 is dominated by antiferromagnetic exchange coupling that results in ground state spin values of S = 3/2 for 1 and 2 and S = 0 for 3. In solution, all four complexes 1–4 show catechol oxidation activity towards 3,5-DTBC. The catalytic activity for the oxidation of 3,5-DTBC in air followed the order 4 < 3 < 1 < 2.

Graphical abstract: Anion coordination selective [Mn3] and [Mn4] assemblies: synthesis, structural diversity, magnetic properties and catechol oxidase activity

Supplementary files

Article information

Article type
Paper
Submitted
24 Mar 2015
Accepted
12 May 2015
First published
18 May 2015

Dalton Trans., 2015,44, 11741-11754

Author version available

Anion coordination selective [Mn3] and [Mn4] assemblies: synthesis, structural diversity, magnetic properties and catechol oxidase activity

M. Pait, M. Shatruk and D. Ray, Dalton Trans., 2015, 44, 11741 DOI: 10.1039/C5DT01157D

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