TY - JOUR
T1 - Coordination interactions in the crystalline lattice of alkaline ions with the polyoxometalate [V12B18O60H6]10- ligand
AU - Hermosilla-Ibáñez, Patricio
AU - Costamagna, Juan
AU - Vega, Andrés
AU - Paredes-García, Verónica
AU - Le Fur, Eric
AU - Spodine, Evgenia
AU - Venegas-Yazigi, Diego
N1 - Funding Information:
Authors acknowledge FONDECYT 1120004 for financial support. This work was done under the LIA-MIF CNRS 836 Collaborative Program. PHI thanks MECESUP UCH 0601 Doctoral Scholarship. PHI also thanks CONICYT AT-24100222 and TT-23120099 Doctoral Scholarships. Authors are indebted to T. Roisnel for X-ray data collection of 1.
Publisher Copyright:
© 2014 Taylor & Francis.
PY - 2014/12/17
Y1 - 2014/12/17
N2 - In the present work, the synthesis and structural characterization of two new polyoxovanadoborate (BVO) frameworks, based on the [V12B18O60H6]10- polyanion, are reported, K(H3O)(enH2)4[V12B18O60H6]·9.60H2O(1) and Li8(NH4)2[V12B18O60H6]·8.02H2O (2). Both compounds are obtained in a mixed valence ratio of 10VIV/2VV. Framework 1 is characterized by potassium ions coordinated by the BVO cluster and ethylenediammonium and hydronium ions as charge-compensating agents. In framework 2, the BVO clusters are coordinating lithium ions and the charge is compensated by ammonium ions. Using the SHAPE 2.1 program, it was possible to calculate the best geometry for the existing lithium and potassium ions. For 2, the lithium ions are five-coordinate, best described by a square pyramid (SPY-5), while the coordination sphere around the potassium ions in 1 are six-coordinate. For 1, the coordination sphere of the existing potassium ions in the framework can be described as trigonal prism (TPR-6). Calculations were also done for a previously reported cluster [Na10[(H2O)V12B18O60H6]·18H2O] (3), in which the sodium ions are six-coordinate but in two different geometries, these being octahedral and TPR-6. The influence of the interactions of the alkali ions with the [V12B18O60H6]10- polyanion, on the vanadate and borate absorption bands observed in the infrared spectra, is discussed.
AB - In the present work, the synthesis and structural characterization of two new polyoxovanadoborate (BVO) frameworks, based on the [V12B18O60H6]10- polyanion, are reported, K(H3O)(enH2)4[V12B18O60H6]·9.60H2O(1) and Li8(NH4)2[V12B18O60H6]·8.02H2O (2). Both compounds are obtained in a mixed valence ratio of 10VIV/2VV. Framework 1 is characterized by potassium ions coordinated by the BVO cluster and ethylenediammonium and hydronium ions as charge-compensating agents. In framework 2, the BVO clusters are coordinating lithium ions and the charge is compensated by ammonium ions. Using the SHAPE 2.1 program, it was possible to calculate the best geometry for the existing lithium and potassium ions. For 2, the lithium ions are five-coordinate, best described by a square pyramid (SPY-5), while the coordination sphere around the potassium ions in 1 are six-coordinate. For 1, the coordination sphere of the existing potassium ions in the framework can be described as trigonal prism (TPR-6). Calculations were also done for a previously reported cluster [Na10[(H2O)V12B18O60H6]·18H2O] (3), in which the sodium ions are six-coordinate but in two different geometries, these being octahedral and TPR-6. The influence of the interactions of the alkali ions with the [V12B18O60H6]10- polyanion, on the vanadate and borate absorption bands observed in the infrared spectra, is discussed.
KW - BVO
KW - Lithium
KW - Mixed valence
KW - Polyoxometalate
KW - VBO
UR - http://www.scopus.com/inward/record.url?scp=84912051735&partnerID=8YFLogxK
U2 - 10.1080/00958972.2014.960407
DO - 10.1080/00958972.2014.960407
M3 - Article
AN - SCOPUS:84912051735
SN - 0095-8972
VL - 67
SP - 3940
EP - 3952
JO - Journal of Coordination Chemistry
JF - Journal of Coordination Chemistry
ER -