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Sensing mechanism elucidation of a chemosensor based on a metal‐organic framework selective to explosive aromatic compounds
Author(s) -
HidalgoRosa Yoan,
TretoSuárez Manuel A.,
Schott Eduardo,
Zarate Ximena,
PáezHernández Dayán
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26404
Subject(s) - chemistry , density functional theory , valence (chemistry) , molecular orbital , photochemistry , atomic orbital , natural bond orbital , computational chemistry , molecule , combinatorial chemistry , organic chemistry , physics , quantum mechanics , electron
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 π‐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.