Supramolecular Mn(II) and Mn(II)/Mn(III) Grid Complexes with [Mn9(μ2-O)12] Core Structures. Structural, Magnetic, and Redox Properties and Surface Studies

A series of [3 × 3] Mn(II)9, antiferromagnetically coupled, alkoxide-bridged, square grid complexes, derived from a group of “tritopic” dihydrazide ligands, is described. The outer ring of eight Mn(II) centers in the grids is isolated magnetically from the central Mn(II) ion, leading to an S = 0 ground state for the ring, and an S = 5/2 ground state overall in each case. Exchange in the Mn(II)8 ring can be represented by a 1D chain exchange model. Rich electrochemistry displayed by these systems has led to the production of Mn(II)/Mn(III) mixed-oxidation-state grids by both electrochemical and chemical means. Structures are reported for [Mn9(2poap)6](C2N3)6·10H2O (1), [Mn9(2poap)6]2[Mn(NCS)4(H2O)]2(NCS)8·10H2O (2), [Mn9(2poapz)6](NO3)6·14.5H2O (3), [Mn9(2popp)6](NO3)6·12H2O (4), [Mn9(2pomp)6](MnCl4)2Cl2·2CH3OH·7H2O (5), and [Mn9(Cl2poap)6](ClO4)9·7H2O (6). Compound 1 crystallized in the tetragonal system, space group P42/n, with a = 21.568(1) A, c = 16.275(1) A, and Z = 2. Compound 2 crystallized in the t...