Step-wise changes in the excited state lifetime of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]− as a function of the number of inner-sphere O-H oscillators
Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Standard
Step-wise changes in the excited state lifetime of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]− as a function of the number of inner-sphere O-H oscillators. / Kofod, Nicolaj; Sørensen, Thomas Just.
I: Dalton Transactions, Bind 53, Nr. 23, 2024, s. 9741–9749 .Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - Step-wise changes in the excited state lifetime of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]− as a function of the number of inner-sphere O-H oscillators
AU - Kofod, Nicolaj
AU - Sørensen, Thomas Just
N1 - Funding Information: The authors thank the Novo Nordisk Foundation, Carlsberg Foundation (CF23-0104), Villum Fonden (Grant No. 14922), the University of Copenhagen and the University of Manchester for support. Publisher Copyright: © 2024 The Royal Society of Chemistry.
PY - 2024
Y1 - 2024
N2 - Lanthanide luminescence is dominated by quenching by high-energy oscillators in the chemical environment. The rate of non-radiative energy transfer to a single H2O molecule coordinated to a Eu3+ ion exceeds the usual rates of emission by an order of magnitude. We know these rates, but the details of these energy transfer processes are yet to be established. In this work, we study the quenching rates of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]− in H2O/D2O mixtures by sequentially exchanging the deuterons with protons. Flash freezing the solutions allows us to identify species with various D/H contents in solution and thus to quantify the energy transfer processes to individual OH-oscillators. This is not possible in solution due to fast exchange in the ensembles present at room temperature. We conclude that the energy transfer processes are accurately described, predicted, and simulated using a step-wise addition of the rates of quenching by each O-H oscillator. This documents the sequential increase in the rate of the energy transfer processes in the quenching of lanthanide luminescence, and further provides a methodology to identify isotopic impurities in deuterated lanthanide systems in solution.
AB - Lanthanide luminescence is dominated by quenching by high-energy oscillators in the chemical environment. The rate of non-radiative energy transfer to a single H2O molecule coordinated to a Eu3+ ion exceeds the usual rates of emission by an order of magnitude. We know these rates, but the details of these energy transfer processes are yet to be established. In this work, we study the quenching rates of [Eu(D2O)9]3+ and [Eu(DOTA)(D2O)]− in H2O/D2O mixtures by sequentially exchanging the deuterons with protons. Flash freezing the solutions allows us to identify species with various D/H contents in solution and thus to quantify the energy transfer processes to individual OH-oscillators. This is not possible in solution due to fast exchange in the ensembles present at room temperature. We conclude that the energy transfer processes are accurately described, predicted, and simulated using a step-wise addition of the rates of quenching by each O-H oscillator. This documents the sequential increase in the rate of the energy transfer processes in the quenching of lanthanide luminescence, and further provides a methodology to identify isotopic impurities in deuterated lanthanide systems in solution.
U2 - 10.1039/d4dt00744a
DO - 10.1039/d4dt00744a
M3 - Journal article
C2 - 38780119
AN - SCOPUS:85194031585
VL - 53
SP - 9741
EP - 9749
JO - Dalton Transactions (Online)
JF - Dalton Transactions (Online)
SN - 1477-9234
IS - 23
ER -
ID: 395089130