abstract
Lanthanide (Ln3+) tetrakis complexes, C[Ln(L)4], are important for applications due to their high quantum yields, solubility, and stability. Their luminescent properties depend on the structure, particularly the coordination polyhedron, the assessment of computational methods for calculating their structures is paramount. Usually, this assessment uses the RMSD of distances in the [Ln(L)4]- complex or {LnO8} polyhedron between crystallographic and calculated structures. However, since ligand field (LF) splitting is highly geometry-dependent, the RMSD between experimental LF splitting and Stark levels (RMSD-LF) offers a more accurate measure for evaluating quantum methods. LF energy eigenvalues were calculated using the simple overlap model (SOM), with geometries optimized by various density functionals. M06 and M06-L functionals, with def2-SVP/MWB52(Eu)/CPCM, demonstrate the best balance in best accuracy and low computational cost, making them suitable for modeling C[Eu(L)4] complexes.
keywords
HYBRID DENSITY FUNCTIONALS; PROSTATE-SPECIFIC ANTIGEN; ENERGY-TRANSFER; EXCITED-STATES; OPTICAL-ABSORPTION; PROGRAM SYSTEM; SPARKLE MODEL; PARAMETERS; TRANSITIONS; INTENSITIES
subject category
Chemistry
authors
Blois, L; Moura, RT Jr; Longo, RL; Malta, OL; Brito, HF; Neto, ANC
our authors
Albano Neto Carneiro Neto
Junior ResearcherProjects
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
This work was supported by Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior. Fundacao para a Ciencia e aTecnologia, LA/P/0006/2020, PTDC/CTMCTM/0340/2021, UIDB/50011/2020, UIDP/50011/2020. Fundacao de Amparo a Pesquisa do Estado de Sao Paulo, 2020/16795- 6, 2021/08111- 2. Conselho Nacional de Desenvolvimento Cientifico e Tecnologico 308000/2022- 6, 308872/2022- 3, 406483/2023-0, 310988/2023-3, and 404742/2024-6.