The role of the Eu3+ 7F1 level in the direct sensitization of the 5D0 emitting level through intramolecular energy transfer

Blois, Lucca; Neto, Albano N. Carneiro; Malta, O.L.; Brito, Hermi F.

doi:10.1016/j.jlumin.2022.118862

Cited by 10 publications

(12 citation statements)

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“…Compounds in Groups II and III also have a great contribution to the energy transfer directly to the Eu(III) 5 D 0 emitting level (sum of pathways 17 and 23, represented by the quantity W T ′), which is a reflection of the 7 F 1 participation in the IET process. 110 Rate Equations and Overall Quantum Yield. Based on schematic energy level diagrams in Figure 5, the population kinetics can be described by the following general rate equations model for all complexes: 5).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Thus, a consequence of these energies differences in the donor states, particularly regarding the T 1 states, is reflected in the backward energy transfer, where the complexes in group I do not have a significant rate while groups II and III do ( W b T is around one order of magnitude lower than W T ); see Figure . Compounds in Groups II and III also have a great contribution to the energy transfer directly to the Eu(III) 5 D 0 emitting level (sum of pathways 17 and 23, represented by the quantity W T′ ), which is a reflection of the 7 F 1 participation in the IET process …”

Section: Resultsmentioning

confidence: 99%

“…The population simulations using eqs 8–12 consider the boundary conditions, which guarantee that the sum of the populations on all energy levels should be constant at any time t . , Thus, the following relationship must be preserved (eq ): where P N ( t ) is the population of state N at time t (0 ≤ t ≤ t f ).…”

Section: Resultsmentioning

confidence: 99%

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Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae

et al. 2022

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In this work, we investigated from a theoretical point of view the dynamics of the energy transfer process from the ligand to Eu(III) ion for 12 isomeric species originating from six different complexes differing by nature of the ligand and the total charge. The cationic complexes present the general formula [Eu(L)(H2O)2]+ (where L = bpcd2– = N,N′-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate; bQcd2– = N,N′-bis(2-quinolinmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate; and bisoQcd2– = N,N′-bis(2-isoquinolinmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate), while the neutral complexes present the Eu(L)(H2O)2 formula (where L = PyC3A3– = N-picolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate; QC3A3– = N-quinolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate; and isoQC3A3– = N-isoquinolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate). Time-dependent density functional theory (TD-DFT) calculations provided the energy of the ligand excited donor states, distances between donor and acceptor orbitals involved in the energy transfer mechanism (R L), spin-orbit coupling matrix elements, and excited-state reorganization energies. The intramolecular energy transfer (IET) rates for both singlet-triplet intersystem crossing and ligand-to-metal (and vice versa) involving a multitude of ligand and Eu(III) levels and the theoretical overall quantum yields (ϕovl) were calculated (the latter for the first time without the introduction of experimental parameters). This was achieved using a blend of DFT, Judd–Ofelt theory, IET theory, and rate equation modeling. Thanks to this study, for each isomeric species, the most efficient IET process feeding the Eu(III) excited state, its related physical mechanism (exchange interaction), and the reasons for a better or worse overall energy transfer efficiency (ηsens) in the different complexes were determined. The spectroscopically measured ϕovl values are in good agreement with the ones obtained theoretically in this work.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae

et al. 2022

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“…The participation of the 7 F 1 J -multiplet in facilitating ET from an antenna to Eu 3+ has been invoked in the literature ,, because the SLJ selection rules forbid transfer involving 7 F 0 . The argument is that at room temperature, where the population of 7 F 1 has been taken as 0.33, for example, in ref , it can act as an effective receiving state.…”

Section: Results and Discussionmentioning

confidence: 99%

“…We present an alternative strategy for attacking this question which utilizes experimental data in conjunction with theory. The compound Eu(TTA) 3 (H 2 O) 2 (TTA = thenoyltrifluoroacetonate) (Figure b) has been chosen for the demonstration of the results because it has been widely studied and applied, ,− and it has been used for illustration in the software JOYSpectra . The temporal variation of the populations of ligand and metal states has been reproduced by a new rate equation model.…”

Section: Introductionmentioning

confidence: 99%

Energy Transfer Mechanism and Quantitative Modeling of Rate from an Antenna to a Lanthanide Ion

et al. 2022

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The excitation energy transfer (ET) pathway and mechanism from an organic antenna to a lanthanide ion has been the subject of discussion for many decades. In the case of europium (Eu 3+ ), it has been suggested that the transfer originates from the ligand singlet state or a triplet state. Taking the lanthanide complex Eu(TTA) 3 (H 2 O) 2 as an example, we have investigated the spectra and luminescence kinetics, mainly at room temperature and 77 K, to acquire the necessary experimental data. We put forward an experimental and theoretical approach to measure the energy transfer rates from the antenna to different Eu 3+ levels using the Dexter formulation. We find that transfer from the ligand singlet state to Eu 3+ may account for the ET pathway, by combined electric dipole–electric dipole (ED–ED) and ED-electric quadrupole (EQ) mechanisms. The contributions from the triplet state by these mechanisms are very small. An independent systems rate equation approach can effectively model the experimental kinetics results. The model utilizes the cooperative processes that take place on the metal ion and ligand and considers S 0 , S 1 , and T 1 ligand states in addition to 7 F 0,1 , 5 D 0 , 5 D 1 , and 5 DJ (= 5 L 6 , 5 D 3 , 5 D 2 combined) Eu 3+ states. The triplet exchange ET rate is estimated to be of the order 10 7 s –1 . The observation of a nanosecond risetime for the Eu 3+ 5 D 1 level does not enable the assignment of the ET route or the mechanism. Furthermore, the 5 D 1 risetime may be contributed by several processes. Observation of its temperature dependence and also that of the ground-state population can supply useful information concerning the mechanism because the change in metal-ion internal conversion rate has a greater effect than changes in singlet or triplet nonradiative rates. A critical comparison is included for the model of Malta employed in the online software LUMPAC and JOYSpectra. The theoretical treatment of the exchange mechanism and its contribution are now being considered.

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Luminescence properties of lanthanide tetrakis complexes as molecular light emitters

Costa,

Blois,

Paolini

et al. 2024

Coordination Chemistry Reviews

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The role of the Eu3+ 7F1 level in the direct sensitization of the 5D0 emitting level through intramolecular energy transfer

Cited by 10 publications

References 58 publications

Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae

Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae

Energy Transfer Mechanism and Quantitative Modeling of Rate from an Antenna to a Lanthanide Ion

Luminescence properties of lanthanide tetrakis complexes as molecular light emitters

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