Coordination Field Tuned Cyanide-Bridged Polynuclear and One-Dimensional Heterobimetallic Complexes: Synthesis, Crystal Structures, and Magnetic Properties

Two mononuclear seven-coordinated macrocycle manganese(II) compounds and four polycyanometallates containing different cyanide groups have been employed as building blocks to assemble cyanide-bridged heterobimetallic complexes, resulting in eight cyanide-bridged FeIII/II-MnII and M-IV-Mn-II (M = Mo, W) complexes {[Mn(L-1)][Fe(1-MeIm)(CN)(5)]}(n) (1), {[Mn(L-2)(H2O)][Fe(1-MeIm)(CN)(5)]}center dot 2H(2)O (2), {[Mn(L-1)(H2O)][Mn(L-1)][Fe(CN)(6)]}n center dot n(CH4O)center dot 3.5nH(2)O (3), {[Mn(L-2)(H2O)](2)][Fe(CN)(6)]}center dot 11H(2)O (4), {[Mn(L-1)(H2O)][Mn(L-1)][Mo(CN)(8)]}n center dot 4nH(2)O (5), {[Mn(L-2)(H2O)]2][Mo(CN)8]}center dot 3.5H(2)O (6), {[Mn(L1)(H2O)][Mn(L1)][W(CN)8]}n center dot 5nH(2)O (7), {[Mn(L-2)(H2O)]2][W(CN)8]}center dot 3H(2)O (8). (L1 = 3,6-diazaoctane-1,8-diamine, L-2 = 3,6-dioxaoctano-1,8-diamine). Single X-ray analysis reveals that complexes 1, 3, 5, and 7 obtained by using [Mn(L1)]2+ as assemble segment can be structurally characterized as a one-dimensional coordination polymer, while the structures of the complexes 2, 4, 6, and 8 with [Mn(L-2)](2+) as the ancillary compound belong to polynuclear entities, indicating that the different coordination field of the N atom or the O atom in the macrocyclic ligands can have an obvious influence on the structure types of the target complexes. Investigation of magnetic properties of complexes 1 and 2 showed the antiferromangetic coupling between the cyanide-bridged low-spin Fe(III) ion and Mn(II) ion. Additional, the weak magnetic interaction between the Mn(II) ions bridged by diamagnetic cyanide building blocks can be found in other complexes.