Sulfoxonium ylides, manageable compounds with an appealing safety profile, adapt to reaction partners like chameleons to their environment, resulting in a variety of useful, and sometimes surprising and unique, reactions.

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 = bpcd^2- = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate; bQcd^2- = N,N'-bis(2-quinolinmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate; and bisoQcd^2- = 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 = PyC3A^3- = N-picolyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetate; QC3A^3- = N-quinolyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetate; and isoQC3A^3- = 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 (ϕ_ovl) 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 (η_sens) in the different complexes were determined. The spectroscopically measured ϕ_ovl values are in good agreement with the ones obtained theoretically in this work.

The complexes [Eu(bpcd)(tta)], [Eu(bpcd)(Coum)], and [Tb(bpcd)(Coum)] [tta = 2-thenoyltrifluoroacetyl-acetonate, Coum = 3-acetyl-4-hydroxy-coumarin, and bpcd = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetate] have been synthesized and characterized from photophysical and thermodynamic points of view. The optical and chiroptical properties of these complexes, such as the total luminescence, decay curves of the Ln(III) luminescence, electronic circular dichroism, and circularly polarized luminescence, have been investigated. Interestingly, the number of coordinated solvent (methanol) molecules is sensitive to the nature of the metal ion. This number, estimated by spectroscopy, is >1 for Eu(III)-based complexes and <1 for Tb(III)-based complexes. A possible explanation for this behavior is provided via the study of the minimum energy structure obtained by density functional theory (DFT) calculations on the model complexes of the diamagnetic Y(III) and La(III) counterparts [Y(bpcd)(tta)], [Y(bpcd)(Coum)], and [La(bpcd)(Coum)]. By time-dependent DFT calculations, estimation of donor-acceptor (D-A) distances and of the energy position of the S₁ and T₁ ligand excited states involved in the antenna effect was possible. These data are useful for rationalizing the different sensitization efficiencies (η_sens) of the antennae toward Eu(III) and Tb(III). The tta ligand is an optimal antenna for sensitizing Eu(III) luminescence, while the Coum ligand sensitizes better Tb(III) luminescence {ϕ_ovl = 55%; η_sens ≥ 55% for the [Tb(bpcd)(Coum)] complex}. Finally, for the [Eu(bpcd)(tta)] complex, a sizable value of g_lum (0.26) and a good quantum yield (26%) were measured.