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 [Mn^II₆Mn^III₄(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 [Mn^III₄Mn^II₆] metallic skeleton that describes three vertex-sharing [Mn^III₂Mn^II₂] butterflies. The structure is closely related to the species [Mn^III₆Mn^II₄(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 Mn^III ions in 4 for Mn^II 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.