Reversible First-Order Single Crystal to Single Crystal Thermal Phase Transition in [(CH3)3CNH3]4[V4O12]

[EN] The well-known compound tetrakis(tert-butylammonium)-cyclo-tetrametavanadate (V), [(CH3)3CNH3]4[V4O12] (1h_RT), which crystallizes in the tetragonal I4/m space group, undergoes an irreversible solid state transformation upon heating, constituting one of the few examples in which the initial and...

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Detalles Bibliográficos
Autores: Vitoria García, Pablo, Wéry, Ana San José, San Felices Mateos, Leire, Bravo García, Laura, Ruiz Bilbao, Estibaliz, Laza Terroba, José Manuel, Vilas Vilela, José Luis, Gutiérrez Zorrilla López, Juan Manuel
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/57354
Acceso en línea:http://hdl.handle.net/10810/57354
Access Level:acceso abierto
Palabra clave:polyoxovanates
SCSC transformations
thermal and structural characterization
Descripción
Sumario:[EN] The well-known compound tetrakis(tert-butylammonium)-cyclo-tetrametavanadate (V), [(CH3)3CNH3]4[V4O12] (1h_RT), which crystallizes in the tetragonal I4/m space group, undergoes an irreversible solid state transformation upon heating, constituting one of the few examples in which the initial and the final stages are structurally characterized by sc-XRD. Now, we observed the ability of the same compound to undergo an additional single-crystal-to-single-crystal (SCSC) transformation upon thermal stimuli, but this time at low temperatures (153 K). Compound 1h_RT contains a discrete unprotonated [V4O12]4− tetrahedral anion in which V and O bridging atoms are coplanar. In both phases, these tetrameric anions are linked through tert-butylammonium cations in an extensive network of hydrogen bonds, but at low temperatures, this phase loses its characteristic O-V-O coplanarity, with the resulting rearrangement of the crystal packing and hydrogen-bond network which provide its reversibility at low temperatures. Again, the initial and final stages have been characterized structurally by sc-XRD.