Тип публикации: статья из журнала
Год издания: 2023
Идентификатор DOI: 10.3390/electronics12122738
Аннотация: <jats:p>For the first time, an extensive theoretical comparative study of the electronic structure and spectra of the η5-cyclopentadienyl half-sandwich [(Cp)(EPh3)], E = Se, Te) organochalcogenides was carried out using direct space electronic structure calculations within hybrid, meta, and meta-hybrid DFT GGA functionals coupled wПоказать полностьюith double-ζ polarized 6-31G* and correlation-consistent triple-zeta cc-pVTZ-pp basis sets. The absence of covalent bonding between the cyclopentadienyl (Cp) ligands and Te/Se coordination centers was revealed. It was found that the chalcogens are partially positively charged and Cp ligands are partially negatively charged, which directly indicates a visible ionic contribution to Te/Se-Cp chemical bonding. Simulated UV–Vis absorption spectra show that all complexes have a UV-active nature, with a considerable shift in their visible light absorption due to the addition of methyl groups. The highest occupied molecular orbitals exhibit π-bonding between the Te/Se centers and Cp rings, although the majority of the orbital density is localized inside the Cp π-system. The presence of the chalcogen atoms and the extension of π-bonds across the chalcogen-ligand interface make the species promising for advanced photovoltaic and light-emitting applications.</jats:p>
Журнал: Electronics
Выпуск журнала: Т. 12, № 12
Номера страниц: 2738
ISSN журнала: 20799292
Место издания: Basel
Издатель: MDPI AG