resumo
This study provides new theoretical insights into the vibrational spectra of Ln(iii) complexes, along the lanthanide series by utilizing the LModeAGen protocol and integrating cutting-edge topological ideas. It provides a quantitative interpretation of the vibrational spectra of [Ln(trensal)] complexes at the B3LYP/MWBn(Ln)/6-311++G** (n from 46 (La) to 60 (Lu)) level using the characterization of normal modes from the local vibrational mode theory. This involves decomposing normal vibrational modes related to the complex formation, distortions in the coordination sphere, and C-H vibrations into local mode contributions, offering particularly promising results aimed at the design of highly luminescent lanthanide complexes. This study also delivers key theoretical insights into the chemical bonding of the coordination sphere of [Ln(trensal)] by combining the local vibrational mode theory and the bond overlap model to achieve relationships between bond properties, including those of the Badger-type. Altogether, we present the theoretical framework necessary to quantitatively interpret the vibrational spectra of [Ln(trensal)] complexes along the lanthanide series and gain a better understanding of the lanthanide-ligand chemical bonds, thereby enhancing our understanding of their chemistry and guiding future design efforts.
palavras-chave
BASIS-SET; STRUCTURAL-CHARACTERIZATION; ELECTRON-DENSITY; PARAMETERS; STRENGTH; TRANSITIONS; INTENSITY; BREAKDOWN; TERMS; III.
categoria
Chemistry; Physics
autores
Machado, FC; Quintano, M; Santos, CV Jr; Neto, ANC; Kraka, E; Longo, RL; Moura, RT Jr
nossos autores
Albano Neto Carneiro Neto
Investigador JúniorOther
Capa
Mediaagradecimentos
FCM thanks CAPES for the Master's scholarship as well as UFPE. MQ, RTMJr, and EK thank the National Science Foundation, Grant CHE 2102461, and SMU's Center for Research Computing for providing generous computational resources. MQ thanks SMU for the postdoctoral fellowship (08/2023-04/2024) and FACEPE for the postdoctoral fellowship BFP-0039-1.06/24 (09/2024-09/2025). RLL thanks CNPq for the PQ-fellowship (Proc. 308000/2022-6). RTMJr thanks the Brazilian National Council for Scientific and Technological Development - CNPq, grant numbers 406483/2023-0, and 310988/2023-3.