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Sensing mechanism elucidation of a europium(III) metal–organic framework selective to aniline: A theoretical insight by means of multiconfigurational calculations

dc.contributor.authorHidalgo-Rosa Y.
dc.contributor.authorTreto-Suárez M.A.
dc.contributor.authorSchott E.
dc.contributor.authorZarate X.
dc.contributor.authorPáez-Hernández D.
dc.date.accessioned2020-09-02T22:20:30Z
dc.date.available2020-09-02T22:20:30Z
dc.date.issued2020
dc.identifier10.1002/jcc.26365
dc.identifier.citation41, 22, 1956-1964
dc.identifier.issn01928651
dc.identifier.urihttps://hdl.handle.net/20.500.12728/4899
dc.descriptionA theoretical procedure, via quantum chemical computations, to elucidate the detection principle of the turn-off luminescence mechanism of an Eu-based Metal-Organic Framework sensor (Eu-MOF) selective to aniline, is accomplished. The energy transfer channels that take place in the Eu-MOF, as well as understanding the luminescence quenching by aniline, were investigated using the well-known and accurate multiconfigurational ab initio methods along with sTD-DFT. Based on multireference calculations, the sensitization pathway from the ligand (antenna) to the lanthanide was assessed in detail, that is, intersystem crossing (ISC) from the S1 to the T1 state of the ligand, with subsequent energy transfer to the 5D0 state of Eu3+. Finally, emission from the 5D0 state to the 7FJ state is clearly evidenced. Otherwise, the interaction of Eu-MOF with aniline produces a mixture of the electronic states of both systems, where molecular orbitals on aniline now appear in the active space. Consequently, a stabilization of the T1 state of the antenna is observed, blocking the energy transfer to the 5D0 state of Eu3+, leading to a non-emissive deactivation. Finally, in this paper, it was demonstrated that the host-guest interactions, which are not taken frequently into account by previous reports, and the employment of high-level theoretical approaches are imperative to raise new concepts that explain the sensing mechanism associated to chemical sensors. © 2020 Wiley Periodicals LLC.
dc.language.isoen
dc.publisherJohn Wiley and Sons Inc.
dc.subjectantenna effect
dc.subjectCASSCF
dc.subjectlanthanide
dc.subjectmetal-organic framework
dc.subjectAniline
dc.subjectAntennas
dc.subjectCalculations
dc.subjectChemical detection
dc.subjectElectronic states
dc.subjectEnergy transfer
dc.subjectLigands
dc.subjectLuminescence
dc.subjectMetal-Organic Frameworks
dc.subjectMolecular orbitals
dc.subjectOrganometallics
dc.subjectHost guest interactions
dc.subjectIntersystem crossing
dc.subjectLuminescence mechanisms
dc.subjectLuminescence quenching
dc.subjectMultireference calculations
dc.subjectQuantum chemical computations
dc.subjectSensing mechanism
dc.subjectTheoretical approach
dc.subjectEuropium compounds
dc.titleSensing mechanism elucidation of a europium(III) metal–organic framework selective to aniline: A theoretical insight by means of multiconfigurational calculations
dc.typeArticle


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