Magnetic and Electrochemical Properties of Lantern-Type Dinuclear Ru(II,III) Complexes with Axial Chloride Ions or Water Molecules

By using [Ru2(O2CC3H7)4Cl]n (1) as a starting material, nBu4N[Ru2(O2CC3H7)4Cl2] (nBu4N+ = tetra(n-butyl)ammonium cation) (2) and [Ru2(O2CC3H7)4(H2O)2]BF4 (3) were prepared. The lantern-type dinuclear structures with axial chloride ions or water molecules were confirmed for 2 and 3 by X-ray crystal structure analyses. The crystal structures of 2 and 3 were compared with that of 1. In the crystal of 2, there were three crystallographically different dinuclear units; the Ru–Ru distances of each unit were 2.3094(3), 2.3046(4), and 2.3034(4) Å, respectively, which were longer than those of 1 (2.281(4) Å) and 3 (2.2584 (7) Å). Temperature dependent magnetic susceptibility measurements were performed for 1 and 2 as well as 3. The effective magnetic moments (µeff) at 300 K were 3.97 (for 1), 4.00 (for 2), and 3.97 µB (for 3), respectively. The decreases in the µeff value were confirmed for all of the complexes due to the large zero-field splitting (D): D = 68 cm−1 for 1, 78 cm−1 for 2, and 60 cm−1 for 3. Cyclic voltammograms measured in CH2Cl2 with a electrolyte of nBu4N(BF4) showed the Ru25+/Ru24+ process at −0.2–−0.4 V (vs. SCE) and the Ru26+/Ru25+ one at 1.3–1.4 V (vs. SCE), of which potentials were confirmed by the DFT calculation for nBu4N[Ru2(O2CC3H7)4Cl2]