Sensing mechanism elucidation of a chemosensor based on ametal-organicframework selective to explosive aromatic compounds

Hidalgo-Rosa, Yoan; Treto-Suarez, Manuel A.; Schott, Eduardo; Zarate, Ximena; Paez-Hernandez, Dayan

Abstract

Theoretical elucidation of the turn-off mechanism of the luminescence of a chemosensor based on a metal-organic framework (MOF) [Zn-2(OBA)(4)(BYP)(2)] (BYP: 4,4 '-bipyridine; H(2)OBA: 4,4 '-oxybis[benzoic acid]), selective to nitrobenzene (NB) via quantum chemical computations, is presented. The electronic structure and optical properties of Zn-MOF were investigated through the combination of density functional theory (DFT) and time-dependent DFT methods. Our results indicate that the fluorescence emission is governed by a linker (BPY)-to-linker (OBA) charge transfer (LLCT) involving orbitals pi-type. Next, the interaction with the analyte was analyzed, where very interesting results were obtained, that is, the lowest unoccupied molecular orbital is now composed of orbitals from NB, which changes the emissive state of the Zn-MOF. This suggests that the LLCT process is blocked, inducing the fluorescence quenching. Otherwise, the Morokuma-Ziegler energy decomposition and natural orbitals for chemical valence on the Zn-MOF-NB interactions were studied in detail, which illustrate the possible channels of charge transfer between Zn-MOF and NB. Finally, we believe that this proposed methodology can be applied to different chemosensor-analyte systems to evidence the molecular and electronic factors that govern the sensing mechanisms.

Más información

Título según WOS: ID WOS:000557546100001 Not found in local WOS DB
Título de la Revista: INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Editorial: Wiley
Fecha de publicación: 2020
DOI:

10.1002/qua.26404

Notas: ISI