Mixed Valence Mn(II)/Mn(III) [3 × 3] Grid Complexes:  Structural, Electrochemical, Spectroscopic, and Magnetic Properties

Mn(II)9 grid complexes with a [Mn9(μ-O)12] core, obtained by self-assembly of a series of tritopic picolinic dihydrazone ligands with Mn(II) salts, have been oxidized by both chemical and electrochemical methods to produce mixed oxidation state systems. Examples involving [Mn(III)3Mn(II)6] and [Mn(III)4Mn(II)5] combinations have been produced. Structures are reported for [Mn9(2poap-2H)6](NO3)6·14H2O (1), [Mn9(2poap-2H)6](ClO4)10·10H2O (3), and [Mn9(Cl2poap-2H)6](ClO4)9·14H2O·3CH3CN (10). Structural studies show distinct contraction of the corner grid sites on oxidation, with overall magnetic properties consistent with the resulting changes in electron distribution. Antiferromagnetic exchange in the outer ring of eight metal centers creates a ferrimagnetic subunit, which undergoes antiferromagnetic coupling to the central metal, leading to S = 1/2 (3) and S = 2/2 (10) ground states. Two moderately intense absorptions are observed on oxidation of the Mn(II) grids in the visible and near-infrared (1000 nm, 700 nm), associated with charge transfer transitions (LMCT, IVCT respectively). Compound 1 crystallized in the monoclinic system, space group P21/n, with a = 21.308(2) Å, b = 23.611(2) Å, c = 32.178(3) Å, β = 93.820(2)°. Compound 3 crystallized in the tetragonal system, space group I4̄, with a = b = 18.44410(10) Å, c = 24.9935(3) Å. Compound 10 crystallized in the triclinic system, space group P1̄, with a = 19.1150(10) Å, b = 19.7221(10) Å, c = 26.8334(14) Å, α = 74.7190(10)°, β = 77.6970(10)°, γ = 64.7770(10)°. The facile oxidation of the Mn(II)9 grids is highlighted in terms of their potential use as molecular based platforms for switching and data storage.