Expanding the Knowledge of the Selective-Sensing Mechanism of Nitro Compounds by Luminescent Terbium Metal-Organic Frameworks through Multiconfigurational ab Initio Calculations
Expanding the Knowledge of the Selective-Sensing Mechanism of Nitro Compounds by Luminescent Terbium Metal-Organic Frameworks through Multiconfigurational ab Initio Calculations
Authors
Hidalgo Rosa, Yoan
Mena Ulecia, Karel
Treto Suarez, Manuel A.
Schott, Eduardo
Paez Hernandez, Dayan
Zarate, Ximena
Mena Ulecia, Karel
Treto Suarez, Manuel A.
Schott, Eduardo
Paez Hernandez, Dayan
Zarate, Ximena
Authors
Date
Datos de publicaciĆ³n:
JOURNAL OF PHYSICAL CHEMISTRY A,Vol.,,2022
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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 Tbbased MOFs sensors is elucidated. The first system is a luminescent Tb-MOF [Tb(BTTA)1.5(H2O)4.5]n (H2BTTA = 2,5-bis(1H-1,2,4triazol-1-yl) terephthalic acid) selective to nitrobenzene (NB), labeled as Tb-1. The second system is {[Tb(DPYT)(BPDC)1/2(NO3)]center dot H2O}n (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 T1 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.