Synthesis and crystal structure of RuIII-supported tungstoantimonate [Sb2W20RuIII2(H2O)2(dmso)6O68]4−

The first RuIII-supported tungstoantimonate [RuII(bpy)3]2[Sb2W20RuIII2(H2O)2(dmso)6O68]·3dmso (bpy=bi-pyridine) (1a) has been successfully isolated as [Ru(bpy)3]2+ (Rubpy) salt by routine synthetic reaction in mixed solutions with dmso and water. Single-crystal X-ray analysis was carried out on 1a, which crystallizes in the triclinic system space group P-1 with a=16.804 (6), b=16.988 (6), c=17.666 (6) Å, α=107.397 (13)°, β=106.883 (13)°, γ=103.616 (12)°. V=4309 (3) Å3, Z=1 with R1=0.0773. The compound 1a reveals the following features: (1) Rubpy is firstly used as an alternative ruthenium-source for the synthesis of Ru-substituted heteropolytungstate; (2) the structure of 1a consists of four RuIII–O–S(CH3)2 and two W–O–S(CH3)2 bonds resulting in an assembly with C2 symmetry; (3) the RuIII ions are linked to two dmso groups via two RuIII–O–S(CH3)2 bonds, which represents the other dmso-coordination mode to RuIII in POM chemistry. The cyclic voltammetry studies of 1a in dmso/H2SO4 (3/1 v/v) at pH 2.5 medium using the glassy carbon electrode as a working electrode show the respective electrochemical behaviors of the W-centers and the Ru-centers within 1a, which could be separated clearly. In addition, the compound 1a exhibits photoluminescence arising from π*−t2g ligand-to-metal transition of Rubpy.

The first RuIII-supported tungstoantimonate [RuII(bpy)3]2[Sb2W20RuIII2(H2O)2(dmso)6O68]·3dmso (bpy=bi-pyridine) (1a) has been synthesized using Ru(bpy)3Cl2 as an alternative ruthenium-source and structurally characterized.Figure optionsDownload as PowerPoint slide