Issue 47, 2021

Oxidation state variation in bis-calix[4]arene supported decametallic Mn clusters

Abstract

The reaction of MnCl2·4H2O, H8L (2,2′-bis-p-tBu-calix[4]arene) and NEt3 in a dmf/MeOH solvent mixture results in the formation of a mixed valent decametallic cluster of formula [MnII6MnIII4(L)23-OH)4(μ-OH)4(MeOH)4(dmf)4(MeCN)2]·MeCN (3). Complex 3 crystallises in the monoclinic space group P21/n with the asymmetric unit comprising half of the compound. Structure solution reveals that the bis-calix[4]arene ligands are arranged such that one TBC[4] moiety in each has undergone inversion in order to accommodate a [MnIII4MnII6] metallic skeleton that describes three vertex-sharing [MnIII2MnII2] butterflies. The structure is closely related to the species [MnIII6MnII4(L)23-O)23-OH)2(μ-OMe)4(H2O)4(dmf)8]·4dmf (4), the major difference being the oxidation level of the Mn ions in the core of the compound. DFT calculations on the full structures reveal that replacing the MnIII ions in 4 for MnII ions in 3 results in a significant decrease in the magnitude of some antiferromagnetic exchange contributions, a switch from ferromagnetic to antiferromagnetic in others, and the loss of significant spin frustration.

Graphical abstract: Oxidation state variation in bis-calix[4]arene supported decametallic Mn clusters

Supplementary files

Article information

Article type
Paper
Submitted
09 Oct 2021
Accepted
19 Nov 2021
First published
19 Nov 2021
This article is Open Access
Creative Commons BY license

Dalton Trans., 2021,50, 17566-17572

Oxidation state variation in bis-calix[4]arene supported decametallic Mn clusters

L. R. B. Wilson, M. Coletta, R. Jose, G. Rajaraman, S. J. Dalgarno and E. K. Brechin, Dalton Trans., 2021, 50, 17566 DOI: 10.1039/D1DT03410C

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