Incorporation of M(H2O)62+ between layers {M(H2O)2Ru2(CO3)4Cl2}n2n− (M = Zn, Mn): syntheses, structures and magnetic properties

Abstract

Isostructural heterometallic diruthenium carbonates KM(H₂O)₆[M(H₂O)₂Ru₂(CO₃)₄Cl₂]·4H₂O [M = Zn (1) and Mn (2)] were synthesized from the reaction of the precursors [Ru₂(CO₃)₄Cl₂]⁵⁻ and transitional metal ions in aqueous solution. Complexes 1 and 2 show layered structures in which Ru₂(II,III) units are linked by four octahedral environment M(H₂O)₂²⁺ ions in a cross fashion and vice versa giving a negative bimetallic square grid layer {M(H₂O)₂Ru₂(CO₃)₄Cl₂}_n³ⁿ⁻. M(H₂O)₆²⁺ ions, linked by K⁺ forming zigzag chain {KM(H₂O)₆}_n³⁺, are located in the void spaces between the layers. The adjacent bimetallic carbonate layers are connected with K–O and K–Cl bonds, and hydrogen bonding, forming a supramolecular 3D framework structure. Their magnetic properties were characterized in detail, and intralayer ferromagnetic coupling between the Ru₂ dimer and Mn²⁺ ion, as well as long-range ordering (T_c = 5.2 K) coexistence of domain movement behavior were observed for complex 2.