Accessing lanthanide-based, <i>in situ</i> illuminated optical turn-on probes by modulation of the antenna triplet state energy

Cosby, Alexia G.; Woods, Joshua J.; Nawrocki, Patrick; Sørensen, Thomas Just; Wilson, Justin J.; Boros, Eszter

doi:10.1039/d1sc02148f

Cited by 24 publications

(21 citation statements)

References 58 publications

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“…No signals from other Ln 3+ ions were detected in any measurements. As expected considering the relative energies of the states involved, ,− we find no evidence of ligand–metal charge transfer or back energy transfer in the systems studied here, see Figure S55.…”

Section: Methodssupporting

confidence: 83%

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d₄)₉]³⁺ Solvates and [Eu·DOTA(MeOH-d₄)]⁻ Complexes

2021

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The trivalent lanthanide ions show optical transitions between energy levels within the 4f shell. All these transitions are formally forbidden according to the quantum mechanical selection rules used in molecular photophysics. Nevertheless, highly luminescent complexes can be achieved, and terbium(III) and europium(III) ions are particularly efficient emitters. This report started when an apparent lack of data in the literature led us to revisit the fundamental photophysics of europium(III). The photophysical properties of two complexes[Eu·DOTA(MeOH-d 4)]− and [Eu(MeOH-d 4)9]3+were investigated in deuterated methanol at five different temperatures. Absorption spectra showed decreased absorbance as the temperature was increased. Luminescence spectra and time-resolved emission decay profiles showed a decrease in intensity and lifetime as the temperature was increased. Having corrected the emission spectra for the actual number of absorbed photons and differences in the non-radiative pathways, the relative emission probability was revealed. These were found to increase with increasing temperature. The transition probability for luminescence was shown to increase with temperature, while the transition probability for light absorption decreased. The changes in transition probabilities were correlated with a change in the symmetry of the absorber or emitter, with an average increase in symmetry lowering absorbance and access to more asymmetric structures increasing the emission rate constant. Determining luminescence quantum yields and the Einstein coefficient for spontaneous emission allowed us to conclude that lowering symmetry increases both. Furthermore, it was found that collisional self-quenching is an issue for lanthanide luminescence, when high concentrations are used. Finally, detailed analysis revealed results that show the so-called “Werts’ method” for calculating radiative lifetimes and intrinsic quantum yields is based on assumptions that do not hold for the two systems investigated here. We conclude that we are lacking a good theoretical description of the intraconfigurational f–f transitions, and that there are still aspects of fundamental lanthanide photophysics to be explored.

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Section: Methodssupporting

confidence: 83%

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d₄)₉]³⁺ Solvates and [Eu·DOTA(MeOH-d₄)]⁻ Complexes

2021

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“…Consideration was given to the utility of semi-empirical calculations of the energy of the key ligand, charge transfer and europium excited states involved in such a quenching process. However, the limited accuracy of such calculations, as exemplied in recent examples using DFT and modied Judd-Ofelt theory, 41,42 meant that such work was not undertaken for these complexes. Electronic energy transfer was examined from a Eu donor to a cyanine dye acceptor with which very good spectral overlap occurs.…”

Section: Discussionmentioning

confidence: 99%

Comparative analysis of lanthanide excited state quenching by electronic energy and electron transfer processes

et al. 2022

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“…For Nd(III), the gap between its emissive state 4 F 3/2 and the antenna triplets is exceeded by an average of ≈2000 cm À1 of the ideal maximum value. Nevertheless, based on the literature, the sensitization in this will not be in the most efficient range, but is possible [73,74].…”

Section: Electronic States Of the Lanthanide Complexes And Sensitizat...mentioning

confidence: 99%

Theoretical study of 8‐hydroxyquinoline derivatives as potential antennas in lanthanide complexes: Photophysical properties and elucidation of energy transfer pathways

Santoyo-Flores

Páez‐Hernández

2022

Int J of Quantum Chemistry

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A series of 8‐hydroxyquinoline derivatives were theoretically characterized and tested as potential antennas in a set of designed lanthanide complexes. The molecular structure and ligand localized nature of the excited states were studied in the framework of the multiconfigurational methods CASSCF/NEVPT2 combined with TD‐DFT‐based approaches, which allow applying a fragmentation scheme in the analysis of the most probable sensitization pathway via antenna effect. The photophysical properties of all the complexes and antennas were carefully analyzed, predicting the most probable energy transfer pathways. Rate constants for photophysical processes involved in the mechanism showed a significant contribution of the vibronic coupling in all cases, and the predominant intersystem‐crossing between S1 and T1 states was demonstrated from the analysis of the nature of the wave function of those states. The energy transfer process described herein demonstrates the possibility of Eu(III) and Nd(III) sensitization by the studied ligands. The proposed methodology gives a complete picture of the antenna excited state dynamics.

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Accessing lanthanide-based, in situ illuminated optical turn-on probes by modulation of the antenna triplet state energy

Abstract: Luminescent lanthanides possess ideal properties for biological imaging, including long luminescent lifetimes and emission within the optical window. Here, we report a novel approach to responsive luminescent Tb(III) probes that...

Cited by 24 publications

References 58 publications

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d₄)₉]³⁺ Solvates and [Eu·DOTA(MeOH-d₄)]⁻ Complexes

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d₄)₉]³⁺ Solvates and [Eu·DOTA(MeOH-d₄)]⁻ Complexes

Comparative analysis of lanthanide excited state quenching by electronic energy and electron transfer processes

Theoretical study of 8‐hydroxyquinoline derivatives as potential antennas in lanthanide complexes: Photophysical properties and elucidation of energy transfer pathways

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Accessing lanthanide-based, in situ illuminated optical turn-on probes by modulation of the antenna triplet state energy

Abstract: Luminescent lanthanides possess ideal properties for biological imaging, including long luminescent lifetimes and emission within the optical window. Here, we report a novel approach to responsive luminescent Tb(III) probes that...

Cited by 24 publications

References 58 publications

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d4)9]3+ Solvates and [Eu·DOTA(MeOH-d4)]− Complexes

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d4)9]3+ Solvates and [Eu·DOTA(MeOH-d4)]− Complexes

Comparative analysis of lanthanide excited state quenching by electronic energy and electron transfer processes

Theoretical study of 8‐hydroxyquinoline derivatives as potential antennas in lanthanide complexes: Photophysical properties and elucidation of energy transfer pathways

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Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d₄)₉]³⁺ Solvates and [Eu·DOTA(MeOH-d₄)]⁻ Complexes

Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d₄)₉]³⁺ Solvates and [Eu·DOTA(MeOH-d₄)]⁻ Complexes