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

Lucinda R. B. Wilson, Marco Coletta, Reshma Jose, Gopalan Rajaraman, Scott J. Dalgarno, Euan K. Brechin

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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.

Original languageEnglish
Pages (from-to)17566-17572
Number of pages7
JournalDalton Transactions
Issue number47
Early online date19 Nov 2021
Publication statusPublished - 21 Dec 2021

ASJC Scopus subject areas

  • Inorganic Chemistry


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