TY - JOUR
T1 - Structure-directing effect of aqueous alkali metal ion (Li+, Na+and K+) clusters on the polyoxoanion configuration in vanadium-molybdenum polyoxometalate solid solutions
AU - Yao, Zhi Yuan
AU - Zhang, Guo Qin
AU - Li, Zi Han
AU - Shen, Lin Jiang
AU - Ren, Xiao Ming
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2021.
PY - 2021/10/7
Y1 - 2021/10/7
N2 - 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 andx= 0.13 for1; M = Na andx= 0.95 for2), 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. Both1and2crystallized in the space groupP1̄ 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 thea+c,c- anda-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. In3, the thermodynamically-stable (H2O)0.3@K6(H2O)12cluster 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.
AB - 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 andx= 0.13 for1; M = Na andx= 0.95 for2), 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. Both1and2crystallized in the space groupP1̄ 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 thea+c,c- anda-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. In3, the thermodynamically-stable (H2O)0.3@K6(H2O)12cluster 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.
UR - http://www.scopus.com/inward/record.url?scp=85115958755&partnerID=8YFLogxK
U2 - 10.1039/d1ce00875g
DO - 10.1039/d1ce00875g
M3 - 文章
AN - SCOPUS:85115958755
SN - 1466-8033
VL - 23
SP - 6533
EP - 6540
JO - CrystEngComm
JF - CrystEngComm
IS - 37
ER -