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Updated: Oct 12, 2025

Stable Aqueous Suspensions of Manganese Ferrite Clusters with Tunable Nanoscale Dimension and Composition
Published on: February 5, 2022
Oxidation state variation in bis-calix[4]arene supported decametallic Mn clusters
Lucinda R B Wilson1, Marco Coletta1, Reshma Jose2
1EastCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh, Scotland, EH9 3FJ, UK. ebrechin@ed.ac.uk.
Abstract:
The reaction of MnCl2·4H2O, H8L (2,2'-bis-p-Bu-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)2(μ3-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)2(μ3-O)2(μ3-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.
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