Wydział Chemii

Claudio Greco

Giorgio Moro

Luca Bertini

Małgorzata Biczysko

Vincenzo Barone

Ugo Cosentino

2014

Journal of Chemical Theory and Computation

10

767-777

10.1021/ct400865b

Naukowa

Angielski

Artykuł

The adiabatic transition energies from the lowest triplet states of four Europium tris β-diketonate/phenantroline complexes have been determined in vacuo and in dicholomethane solution by the ΔSCF approach at the density functional theory level, using the PBE1PBE and the CAM-B3LYP hybrid functionals. The calculated adiabatic transition energies have been compared with the experimental 0–0 transitions of each complex determined from phosphorescence spectra of the corresponding Gd³⁺ complexes and followed by direct comparison between simulated and experimental spectra line shapes. For compound 1, the Eu(TTA)₃Phen system, triplet states other than the lowest one and conformational isomers other than the one present in the crystallographic structure have been considered. In the crystallographic structure, this compound presents three quasi-degenerate low energy triplet states, differing for the TTA ligand where the two unpaired electrons are localized and showing close adiabatic transition energies. For compound 1, the lowest triplet states of the four investigated conformational isomers show similar characteristics and close adiabatic transition energies. On the basis of these results, an investigation of compounds 2–4 (Eu(Br-TTA)₃Phen, Eu(DTDK)₃Phen, and Eu(MeT-TTA)₃) has been performed by considering only the isomer present in the crystallographic structure and only the lowest triplet state of each compound. For compounds 1–3, the energies of the lowest triplet states calculated by both functionals in solution including zero-point energy corrections well reproduce the experimental trends as well as the values of the adiabatic transition energies: CAM-B3LYP, the best performing functional, provides energies of the lowest triplet state with deviations from experiments lower than 1200 cm^–1. Also, the calculated vibrationally resolved phosphorescence spectra and UV–vis absorptions well reproduce the main features of their experimental counterparts. Significant differences between calculated and experimental results are observed for compound 4, for which difficulties in the experimental determination of the triplet state energy were encountered: our results show that the negligible photoluminescence quantum yield of this compound is due to the fact that the energy of the most stable triplet state is significantly lower than that of the resonance level of the Europium ion, and thus the energy transfer process is prevented.These results confirm the reliability of the adopted computational approach in calculating the energy of the lowest triplet state energy of these systems, a key parameter in the design of new ligands for lanthanide complexes presenting large photoluminescence quantum yields.

Ligands, Molecular structure, Phase transitions, Quantum mechanics, Time dependant density functional theory

http://dx.doi.org/10.1021/ct400865b

https://www.acs.org/content/acs/en.html