Expanding the Knowledge of the Selective-Sensing Mechanism of Nitro Compounds by Luminescent Terbium Metal-Organic Frameworks through Multiconfigurational ab Initio Calculations
Date
Authors
MENA ULECIA, KAREL
Hidalgo-Rosa, Yoan
Mena-Ulecia, Karel
Treto-Suárez, Manuel Alejandro
Schott V, Eduardo
Páez-Hernández, Dayán
Zárate, Ximena P.
Hidalgo-Rosa, Yoan
Mena-Ulecia, Karel
Treto-Suárez, Manuel Alejandro
Schott V, Eduardo
Páez-Hernández, Dayán
Zárate, Ximena P.
Authors
Date
Datos de publicación:
10.1021/acs.jpca.2c05468
Keywords
Calculations - Electronic States - Excited States - Luminescence - Metal-organic Frameworks - Organic Polymers - Quenching - Rate Constants - 'current - Ab Initio Calculations - Analytes - Excited-state Dynamics - Luminescence Quenching - Metalorganic Frameworks (mofs) - Nitro-compounds - Selective Sensing - Sensing Mechanism - Terephthalic Acids - Antennas
Collections
Abstract
The current research shows that the excited-state dynamics of the antenna ligand, both in the interacting system sensor/analyte and in the sensor without analyte, is a safe tool for elucidating the detection principle of the luminescent lanthanide-based metal-organic framework sensors. In this report the detection principle of the luminescence quenching mechanism in two Tb-based MOFs sensors is elucidated. The first system is a luminescent Tb-MOF [Tb(BTTA)<inf>1.5</inf>(H<inf>2</inf>O)<inf>4.5</inf>]<inf>n</inf>(H<inf>2</inf>BTTA = 2,5-bis(1H-1,2,4-triazol-1-yl) terephthalic acid) selective to nitrobenzene (NB), labeled as Tb-1. The second system is {[Tb(DPYT)(BPDC)<inf>1/2</inf>(NO<inf>3</inf>)]·H<inf>2</inf>O}<inf>n</inf>(DPYT = 2,5-di(pyridin-4-yl) terephthalic acid, BPDC = biphenyl-4,4?-dicarboxylic acid), reported as a selective chemical sensor to nitromethane (NM) in situ, labeled as Tb-2. The luminescence quenching of the MOFs is promoted by intermolecular interactions with the analytes that induce destabilization of the T<inf>1</inf>electronic state of the linker "antenna", altering thus the sensitization pathways of the Tb atoms. This study demonstrates the value of host-guest interaction simulations and the rate constants of the radiative and nonradiative processes in understanding and elucidating the sensing mechanism in Ln-MOF sensors. © 2022 Elsevier B.V., All rights reserved.
Description
Keywords
Calculations , Electronic States , Excited States , Luminescence , Metal-organic Frameworks , Organic Polymers , Quenching , Rate Constants , 'current , Ab Initio Calculations , Analytes , Excited-state Dynamics , Luminescence Quenching , Metalorganic Frameworks (mofs) , Nitro-compounds , Selective Sensing , Sensing Mechanism , Terephthalic Acids , Antennas
Citation
10.1021/acs.jpca.2c05468