Novel Doped Tungstovanadate and Molybdovanadate with Bi-antimony-Capped Keggin Structure

Abstract

Three novel V-centred Keggin-based compounds containing cap-shaped Sb atoms: (HDMF)2[(VO4)W5.65V7.74Sb2.61O36.77]·6H2O (1), [Co(phen)3]2[(VO4)Mo9.58V2.42Sb2O36]·6H2O (2) and [Ni(phen)2(H2O)]2[(VO4)Mo8V4Sb2O36]·2H2O (3) (DMF = dimethylformamide; phen = 1,10-phenanthroline) have been synthesized and characterized. X-ray diffraction analysis revealed that compound 1 consists of an unusually one-dimensional 12-tungstovanadate Keggin-based polymer, in which the reduced tungstovanadate Keggin species are stabilized by introducing capping {VO} and {Sb} groups and then linked into chains via V(Sb)–O–V(Sb) interactions. Both 2 and 3 are built from secondary metal–ligand groups (Co-phen for 2, Ni-phen for 3) and 12-molybdovanadate doped Keggin-type cores with two antimony atoms capping two opposite sites. The anion in 3 represents a bi-capped and bi-supported Keggin-type structure. The electrochemical properties of 2- and 3-modified carbon paste electrodes (2-CPE and 3-CPE) are also studied.