In this study, optical spectroscopy, excited state dynamics and the Tb³⁺→Eu³⁺ energy transfer in particular have been investigated in detail (both from the theoretical and experimental point of view) in eulytite double phosphate hosts A₃Tb(PO₄)₃ (A=Sr, Ba) doped with Eu³⁺. It has been found that the energy transfer is strongly assisted by fast migration in the donor Tb³⁺ subset. Moreover, the transfer rates and efficiencies depend significantly on the nature of the divalent elements present in the structure and hence on the distances between nearest neighboring Tb³⁺ and Eu³⁺. It is shown that the competition between quadrupole-quadrupole and exchange interaction is crucial in accounting for the transfer rates.

Thin film solar cells have reached commercial maturity and extraordinarily high efficiency that make them competitive even with the cheaper Chinese crystalline silicon modules. However, some issues (connected with presence of toxic and/or rare elements) are still limiting their market diffusion. For this reason new thin film materials, such as Cu₂ZnSnS₄ or SnS, have been introduced so that expensive In and Te, and toxic elements Se and Cd, are substituted, respectively, in CuInGaSe₂ and CdTe. To overcome the abundance limitation of Te and In, in recent times new thin film materials, such as Cu₂ZnSnS₄ or SnS, have been investigated. In this paper we analyze the limitations of SnS deposition in terms of reproducibility and reliability. SnS deposited by thermal evaporation is analyzed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. The raw material is also analyzed and a different composition is observed according to the different number of evaporation (runs). The sulfur loss represents one of the major challenges of SnS solar cell technology.

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 coordination features and signaling of a L-lactate ion by a [Tb(bpcd)]⁺ (bpcd = N,N′-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N′-diacetate) complex have been investigated by means of a combination of techniques, including total luminescence, calorimetry and circularly polarized luminescence. The L-lactate/[Tb(bpcd)]⁺ association constant, determined by both luminescence titration and isothermal titration calorimetry, indicates a weak interaction (log K = 1.3–1.45) between the analyte and both enantiomers of the complex. The theoretical DFT calculations suggest that the most likely coordination of L-lactate to the possible stereoisomers of the [Tb(S,S-bpcd)]⁺ complex (trans-O,O or trans-N_py,N_py) is one involving a hydroxyl group. The results of [Tb(rac-bpcd)]⁺ as a chiroptical luminescent probe of L-lactate underline the peculiar role of the chiral 1,2-diaminocyclohexane (DACH) backbone. Indeed, the target anion is capable of inducing CPL activity in the racemic mixture of Tb complexes containing DACH-based ligands. The same is not observed for the achiral analogue [Tb(bped)]⁺ (bped = N,N′-bis(2-pyridylmethyl)ethylenediamine-N,N′-diacetate) complex, likely because of the flexibility of the ethylenic group which allows an interconversion between different isomers which produces a null net CPL activity. Thanks to the differential quantum yield of the two diastereomeric species (R,R)-L and (S,S)-L, one can use the racemic complex to reveal L-lactate by measuring the induced CPL spectrum. Interestingly, this has been demonstrated in a commercial complex solution for medical use, containing several electrolytes, namely Ringer's lactate.

Each enantiopure europium(III) and samarium(III) nitrate and triflate complex of the ligand L, with L = N,N′-bis(2-pyridylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine ([LnL(tta)₂]·NO₃ and [LnL(tta)₂(H₂O)]·CF₃SO₃, where tta = 2-thenoyltrifluoroacetylacetonate) has been synthesized and characterized from a spectroscopic point of view, using a chiroptical technique such as electronic circular dichroism (ECD) and circularly polarized luminescence (CPL). In all cases, both ligands are capable of sensitizing the luminescence of both metal ions upon absorption of light around 280 and 350 nm. Despite small differences in the total luminescence (TL) and ECD spectra, the CPL activity of the complexes is strongly influenced by a concurrent effect of the solvent and counterion. This particularly applies to europium(III) complexes where the CPL spectra in acetonitrile can be described as a weighed linear combination of the CPL spectra in dichloromethane and methanol, which show nearly opposite signatures when their ligand stereochemistries are the same. This phenomenon could be related to the presence of equilibria interconverting solvated, anion-coordinated complexes and isomers differing by the relative orientation of the tta ligands. The difference between some bond lengths (M–N bonds, in particular) in the different species could be at the basis of such an unusual CPL activity.