Abstract
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)(H(2)O)(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)(H(2)O)(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.