Step-wise changes in the excited state lifetime of [Eu(DO)] and [Eu(DOTA)(DO)] as a function of the number of inner-sphere O-H oscillators

Lanthanide luminescence is dominated by quenching by high-energy oscillators in the chemical environment. The rate of non-radiative energy transfer to a single H 2 O molecule coordinated to a Eu 3+ 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(D 2 O) 9 ] 3+ and [Eu(DOTA)(D 2 O)] − in H 2 O/D 2 O 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. We use time-resolved emission spectroscopy to directly observe mono-protonated species of [Eu(D 2 O) 9 ] 3+ and [Eu(DOTA)(D 2 O)] − . This proves that the sequential OH quenching pathways can be accurately predicted and modelled.