Vanadium Polyoxoanions within Coordination Polymers Based on a Macrocyclic Nickel Complex: Structural Diversities and Single-Crystal to Single-Crystal Transformation.

Ou, Guang‐Chuan; Yuan, Xian‐You; Li, Zhi‐Zhang; Li, Wen‐Yi; Zeng, Fei; Deng, Ji‐Hua; Zhong, Di‐Chang

Five three-dimensional (3D) coordination polymers, {(NiL)[(NiL)(V16O42)]} n ·2 nH2O ( 1), [(NiL)3(VO3)6] n ·5 nH2O ( 2), [(NiL)3(V6O18)] n ·7 nH2O ( 3), [(NiL)3(V8O23)] n ( 4), and [(NiL)4(V10O29)] n ( 5), have been obtained by the reaction of the macrocyclic nickel complex [NiL](ClO4)2 (L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions. Single-crystal X-ray diffraction analyses revealed that the [VO3]- anion assumes diverse species and structures in these five coordination polymers, including the [V16O42] n4 n- sheet, [V6O18]6- ring, [VO3] nn- chain, [VO3] nn- sheet, and [V10O29] n8 n- chain. The [V16O42] n4 n- sheets, [V6O18]6- rings, [VO3] nn- chains, [VO3] nn- sheets, and [V10O29] n8 n- chains are linked together through [NiL]2 bridges to form the 3D frameworks of 1- 5. The single-crystal to single-crystal transformation between 2 and desolvated 2 was successfully realized. Electrochemical measurements indicate that 2 and 4 are potential catalysts for water splitting.

MACROMOLECULES; VANADIUM; POLYMERS; SINGLE crystals; CHELATES

European Journal of Inorganic Chemistry, 2016, Vol 2016, Issue 21, p3500

1434-1948

Academic Journal

10.1002/ejic.201600284