Tb3+Photophysics: Mapping Excited State Dynamics of [Tb(H2O)9]3+Using Molecular Photophysics
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Tb3+Photophysics : Mapping Excited State Dynamics of [Tb(H2O)9]3+Using Molecular Photophysics. / Kofod, Nicolaj; Sørensen, Thomas Just.
I: Journal of Physical Chemistry Letters, Bind 13, Nr. 51, 2022, s. 11968-11973.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Tb3+Photophysics
T2 - Mapping Excited State Dynamics of [Tb(H2O)9]3+Using Molecular Photophysics
AU - Kofod, Nicolaj
AU - Sørensen, Thomas Just
N1 - Publisher Copyright: © 2022 American Chemical Society. All rights reserved.
PY - 2022
Y1 - 2022
N2 - The study of optical transitions in lanthanide(III) ions has evolved separately from molecular photophysics, but the framework still applies to these forbidden transitions. In this study, a detailed photophysical characterization of the [Tb(H2O)9]3+aqua ion was performed. The luminescence quantum yield (φlum), excited state lifetime (τobs), radiative (krA) and nonradiative (knr) rate constants, and oscillator strength (f) were determined for Tb(CF3SO3)3in H2O/D2O mixtures in order to map the radiative and nonradiative transition probabilities. It was shown that the intense luminescence observed from Tb3+compared to other Ln3+ions is not due to a higher transition probability of emission but rather due to a lack of quenching, quantified by quenching to O-H oscillators in the aqua ion of kq(OH) = 2090 s-1for terbium and kq(OH) = 8840 s-1for europium. In addition, the Horrocks method of determining inner-sphere solvent molecules has been revisited, and it was concluded that the Tb3+is 9-coordinated in aqueous solution.
AB - The study of optical transitions in lanthanide(III) ions has evolved separately from molecular photophysics, but the framework still applies to these forbidden transitions. In this study, a detailed photophysical characterization of the [Tb(H2O)9]3+aqua ion was performed. The luminescence quantum yield (φlum), excited state lifetime (τobs), radiative (krA) and nonradiative (knr) rate constants, and oscillator strength (f) were determined for Tb(CF3SO3)3in H2O/D2O mixtures in order to map the radiative and nonradiative transition probabilities. It was shown that the intense luminescence observed from Tb3+compared to other Ln3+ions is not due to a higher transition probability of emission but rather due to a lack of quenching, quantified by quenching to O-H oscillators in the aqua ion of kq(OH) = 2090 s-1for terbium and kq(OH) = 8840 s-1for europium. In addition, the Horrocks method of determining inner-sphere solvent molecules has been revisited, and it was concluded that the Tb3+is 9-coordinated in aqueous solution.
U2 - 10.1021/acs.jpclett.2c03506
DO - 10.1021/acs.jpclett.2c03506
M3 - Journal article
C2 - 36534789
AN - SCOPUS:85144405528
VL - 13
SP - 11968
EP - 11973
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 51
ER -
ID: 333304168