Ligand-directed synthesis of {MnIII5} twisted bow-ties

Heras Ojea, María José and Hay, Moya A. and Cioncoloni, Giacomo and Craig, Gavin A. and Wilson, Claire and Shiga, Takuya and Oshio, Hiroki and Symes, Mark D. and Murrie, Mark (2017) Ligand-directed synthesis of {MnIII5} twisted bow-ties. Dalton Transactions, 46 (34). pp. 11201-11207. ISSN 1477-9234 (https://doi.org/10.1039/C7DT02430D)

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Abstract

Two isostructural polymetallic complexes [MnIII5(μ3-O)2(CH3COO)4(L1)4]− and [MnIII5(μ3-O)2(CH3COO)4(L2)4]− have been synthesised by using two Schiff base ligands derived from 3,5-diamino-1,2,4-triazole, following two different preparative routes, either using the pre-formed ligand (for L1) or via a metal-mediated template synthesis (for L2). The {MnIII5} structure is unusual, being based on two corner-sharing perpendicular {Mn3} triangles forming a twisted bow-tie. The magnetic studies reveal antiferromagnetic coupling between Mn(iii) ions while electrochemical experiments are consistent with a quasi-reversible Mn(iii)↔Mn(iv) redox process at the central manganese ion.