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Title: Template-free cyclic hexavanadate: Synthesis, characterization, solid-state structure, and solution-state dynamics

Abstract

A novel hexavanadate–organic hybrid material of the formula [NH 4] 2[V 62-O) 6(O) 4(PDC) 6] (PDC = 2,6-pyridinedicarboxylate) has been prepared in dilute nitric acid under hydrothermal reaction conditions. The product was characterized by single crystal and powder X-ray diffraction, FTIR, UV–Vis, Raman, and thermogravimetric analyses in the solid state, and small angle X-ray scattering, ESI-MS, NMR ( 1H, 13C, 51V), and Raman spectroscopic techniques in aqueous solution. The crystal structure revealed a rare structure type in vanadium chemistry which crystallizes in the monoclinic space group P2 1/n and consists of a cyclic polyoxovanadate core with edge-capped tetrahedral and octahedral vanadium centers. The “hollow” polyoxovanadate is stabilized by a PDC ligand on each metal center, and ammonium ions charge balance the anionic core and form hydrogen bonding interactions with the hexavanadate units. Solution-state studies showed that the structural unit observed in the solid state hydrolyzes upon dissolution in water, resulting in a symmetric dimer bearing similar ligand sets. Catalytic experiments on the photodecomposition of crystal violet, rhodamine B, methylene blue, and rhodamine 6G showed ≥93% degradation of the dyes under UV light irradiation upon addition of the vanadium complex.

Authors:
; ; ; ORCiD logo; ORCiD logo; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566476
DOE Contract Number:  
SC0001089
Resource Type:
Journal Article
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 169; Journal Issue: C; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Batrice, Rami J., Wacker, Jennifer N., Glass, Elliot N., Jilani, Safia Z., Tong, YuYe J., Nyman, May, and Knope, Karah E. Template-free cyclic hexavanadate: Synthesis, characterization, solid-state structure, and solution-state dynamics. United States: N. p., 2019. Web. doi:10.1016/j.poly.2019.05.014.
Batrice, Rami J., Wacker, Jennifer N., Glass, Elliot N., Jilani, Safia Z., Tong, YuYe J., Nyman, May, & Knope, Karah E. Template-free cyclic hexavanadate: Synthesis, characterization, solid-state structure, and solution-state dynamics. United States. doi:10.1016/j.poly.2019.05.014.
Batrice, Rami J., Wacker, Jennifer N., Glass, Elliot N., Jilani, Safia Z., Tong, YuYe J., Nyman, May, and Knope, Karah E. Sun . "Template-free cyclic hexavanadate: Synthesis, characterization, solid-state structure, and solution-state dynamics". United States. doi:10.1016/j.poly.2019.05.014.
@article{osti_1566476,
title = {Template-free cyclic hexavanadate: Synthesis, characterization, solid-state structure, and solution-state dynamics},
author = {Batrice, Rami J. and Wacker, Jennifer N. and Glass, Elliot N. and Jilani, Safia Z. and Tong, YuYe J. and Nyman, May and Knope, Karah E.},
abstractNote = {A novel hexavanadate–organic hybrid material of the formula [NH4]2[V6(µ2-O)6(O)4(PDC)6] (PDC = 2,6-pyridinedicarboxylate) has been prepared in dilute nitric acid under hydrothermal reaction conditions. The product was characterized by single crystal and powder X-ray diffraction, FTIR, UV–Vis, Raman, and thermogravimetric analyses in the solid state, and small angle X-ray scattering, ESI-MS, NMR (1H, 13C, 51V), and Raman spectroscopic techniques in aqueous solution. The crystal structure revealed a rare structure type in vanadium chemistry which crystallizes in the monoclinic space group P21/n and consists of a cyclic polyoxovanadate core with edge-capped tetrahedral and octahedral vanadium centers. The “hollow” polyoxovanadate is stabilized by a PDC ligand on each metal center, and ammonium ions charge balance the anionic core and form hydrogen bonding interactions with the hexavanadate units. Solution-state studies showed that the structural unit observed in the solid state hydrolyzes upon dissolution in water, resulting in a symmetric dimer bearing similar ligand sets. Catalytic experiments on the photodecomposition of crystal violet, rhodamine B, methylene blue, and rhodamine 6G showed ≥93% degradation of the dyes under UV light irradiation upon addition of the vanadium complex.},
doi = {10.1016/j.poly.2019.05.014},
journal = {Polyhedron},
issn = {0277-5387},
number = C,
volume = 169,
place = {United States},
year = {2019},
month = {9}
}