Anionic ligand exchange on ZrPO(4)Cl(dmso): alkoxide and carboxylate derivatives

This paper reports the preparation and characterization of a series of organic derivatives of ZrPO(4)Cl(CH(3))(2)SO obtained by topotactic anion exchange of chloride ligands with several n-alkoxide (RO) and carboxylate groups (RCOO). Exchange with alkoxides, with an alkyl chain length from 2 to 8 carbon atoms, gave products of general formula ZrPO(4)RO(CH(3))(2)SO. In these derivatives alkoxide groups, covalently bonded to zirconium atoms via Zr-O bonds, point toward the interlayer region. Carboxylate derivatives, of general formula ZrPO(4)[(RCOO)(CH(3))(2)SO](1)(-)(x)(OH H(2)O)(x), were obtained using benzoate (x = 0), nitrobenzoate (x = 0.3), and phenylacetate (x = 0.2) groups. The thermal behavior of these organic derivatives is discussed. Due to this reactivity, ZrPO(4)Cl(CH(3))(2)SO is an attractive precursor for materials chemistry.