Syntheses, Crystal Structures and Magnetic Properties of Cyanide- and Phenolate-Bridged Two-Dimensional M(II)-Mn(III) (M=Ru and Os) Complexes

Two new M(II)-Mn(III) complexes {[Mn(III)(salen)](4)[Mn(III)(salen)(H2O)](2)[M(II)(CN)(6)]}(ClO4)(2)center dot 2H(2)O (M=Ru (1) and Os (2)) (salen(2-)=N,N'-ethylenebis(salicylideneaminato)dianion) have been synthesized based on [Mn(III)(salen)](+) segment and hexacyanide-containing building blocks [M(II)(CN)(6)](4-). Single crystal X-ray diffraction analyses show that both complexes are isostructurally two-dimensional (2D) structures in which cyanide -bridged heptanuclear [Mn(III)(6)M(II)](2+) units are linked together by double phenolate bridges. Magnetic studies show that they are abnormal antiferromagnetic through the double phenolate bridges with the magnetic coupling constant J=-0.340 cm(-1) for 1 and -0.561 cm(-1) for 2 based on the spin exchange Hamiltonian (H) over cap=-2J(MnMn)(S) over cap (Mn1)(S) over cap (Mn2). CCDC:1447244, 1; 1447245, 2.