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Sensing Mechanism Elucidation of a Chemosensor Based on a Metal-Organic Framework (MOF) Selective to Explosive Aromatic Compounds
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  • Yoan Hidalgo-Rosa,
  • Manuel A. Treto-Suarez,
  • Eduardo Schott,
  • Ximena Zarate,
  • Dayan Paez-Hernandez
Yoan Hidalgo-Rosa
Universidad Andres Bello

Corresponding Author:[email protected]

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Manuel A. Treto-Suarez
Universidad Andres Bello
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Eduardo Schott
Pontificia Universidad Catolica de Chile
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Ximena Zarate
Universidad Andres Bello
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Dayan Paez-Hernandez
Universidad Andres Bello
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Theoretical elucidation of the turn-off mechanism of the luminescence of a chemosensor based on a metal-organic framework (MOF) [Zn2(OBA)4(BYP)2] (BYP: 4,4’-bipyridine; H2OBA: 4,4’-oxybis(benzoic acid)), selective to nitrobenzene 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, interaction with the analyte was analyzed, where very interesting results were obtained, i.e. the LUMO is now composed by orbitals from nitrobenzene, which changes the emissive state of the Zn-MOF. This fact suggests that the LLCT process is blocked, inducing then the fluorescence quenching. Otherwise, the Morokuma-Ziegler energy decomposition and NOCV (Natural Orbitals for Chemical Valence) on the Zn-MOF-nitrobenzene interactions were studied in detail, which illustrate the possible channels of charge transfer between Zn-MOF and nitrobenzene. 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.
13 Apr 2020Submitted to International Journal of Quantum Chemistry
13 Apr 2020Submission Checks Completed
13 Apr 2020Assigned to Editor
05 May 2020Reviewer(s) Assigned
09 May 2020Review(s) Completed, Editorial Evaluation Pending
11 May 2020Editorial Decision: Revise Major
09 Jun 20201st Revision Received
09 Jun 2020Submission Checks Completed
09 Jun 2020Assigned to Editor
08 Jul 2020Reviewer(s) Assigned
08 Jul 2020Review(s) Completed, Editorial Evaluation Pending
08 Jul 2020Editorial Decision: Accept