High spin molecules: (NBun4)2[Mn8O4(O2CPh)12(Et2mal)2(H2O)2], a mixed-valence managenese(II/III) aggregate with dicarboxylate ligation, an unusual linked-butterfly structure, and an S= 3 ground state

Abstract

Treatment of (NBuⁿ₄)[Mn₄O₂(O₂CPh)₉(H₂O)] with Na₂(Et₂mal) in MeCN leads to a nuclearity and oxidation level change to give (NBuⁿ₄)₂[Mn₈O₄(O₂CPh)₁₂(Et₂mal)₂(H₂O)₂]1; the crystal structure and magnetochemical studies show the core of the anion to have a unique topology consisting of two linked [Mn₄O₂] butterfly units and to possess an S = 3 ground state, respectively.