Issue 37, 2021

Structure-directing effect of aqueous alkali metal ion (Li+, Na+ and K+) clusters on the polyoxoanion configuration in vanadium–molybdenum polyoxometalate solid solutions

Abstract

In a structural chemistry context, the dense packing and the structure-directing agent (SDA) often play a crucial role in the formation of the desired crystal structure. Herein, we present two isomorphous decavanadate-type polyoxometalates, M2(NH4)4−x[V10−xMoxO28]·10H2O (M = Li and x = 0.13 for 1; M = Na and x = 0.95 for 2), prepared by solution evaporation under ambient conditions and characterized by the techniques of EDS, ICP-MS, TG, XPS, X-band EPR spectroscopy, and X-ray single crystal and powder diffractions. Both 1 and 2 crystallized in the space group P[1 with combining macron] with analogous cell parameters, containing thermodynamically stable [M2(H2O)10]2+ (M = Li or Na) clusters, NH4+ ions and decavanadate-type polyoxoanions with V5+ and Mo6+ ions. The polyoxoanions and {M2(H2O)10}2+ cluster cations, owing to their comparable dimensions, arrange alternately to form dense packing along the a + c, c- and a-axis directions. As earlier reported, however, [(H2O)0.3@K6(H2O)12]H4.45[PV7.45Mo4.55O40]·11H2O (3) crystallizes in a CsCl-type dense packing structure under analogous crystal growth conditions. In 3, the thermodynamically-stable (H2O)0.3@K6(H2O)12 cluster cation and Keggin-type {Mo4.55V7.45PO40}10.45− polyoxoanion have comparable dimensions. This study clearly reveals the structure-directing effect of thermodynamically-stable aqueous alkali metal ion clusters, initially formed in the reaction mixture, on a polyoxoanion configuration in vanadium–molybdenum polyoxometalate solid solutions.

Graphical abstract: Structure-directing effect of aqueous alkali metal ion (Li+, Na+ and K+) clusters on the polyoxoanion configuration in vanadium–molybdenum polyoxometalate solid solutions

Supplementary files

Article information

Article type
Paper
Submitted
02 Jul 2021
Accepted
04 Aug 2021
First published
05 Aug 2021

CrystEngComm, 2021,23, 6533-6540

Structure-directing effect of aqueous alkali metal ion (Li+, Na+ and K+) clusters on the polyoxoanion configuration in vanadium–molybdenum polyoxometalate solid solutions

Z. Yao, G. Zhang, Z. Li, L. Shen and X. Ren, CrystEngComm, 2021, 23, 6533 DOI: 10.1039/D1CE00875G

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