title: Application of time-dependent density functional theory and optical spectroscopy toward the rational design of novel 3,4,5-triaryl-1-R-1,2-diphospholes.
abstract: Twenty 3,4,5-triaryl-1-R-1,2-diphospholes were studied within the framework of density functional theory (DFT) and experimentally by UV/vis spectroscopy to check their suitability for opto-electronic applications. Time-dependent DFT (TD-DFT) calculations employing the PBE0 hybrid density functional combined with moderately sized def-TZVP basis set were shown to excellently reproduce the experimental absorption spectra of various 1,2-diphospholes. Frontier molecular orbital analysis reveals that HOMO and LUMO are mainly localized on the diphosphole ring and, to some extent, on the aryl moieties. The HOMO-LUMO energy gap can be easily tuned by variation of substituents introduced in para-positions of the aryl moieties and, to a lesser extent, by modification of the R group at phosphorus atom. As a result, both position and intensity of the absorption bands with highest wavelength are strongly influenced by the above structural changes. The UV-spectra simulations reveal that the introduction of donor groups like para-OMe, para-NMe2, and para-N(H)Ph, which are in n-π conjugation with the aryl moieties, should result in absorption of visible light by the corresponding 1,2-diphospholes, thus making them promising candidates for new functional materials.
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russia. zverevaelena@ymail.com
authors.forename: Elena E
authors.initials: EE
authors.lastname: Zvereva
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.forename: Sergey A
authors.initials: SA
authors.lastname: Katsyuba
authors.forename: Timur I
authors.initials: TI
authors.lastname: Burganov
authors.forename: Almaz A
authors.initials: AA
authors.lastname: Zagidullin
authors.forename: Vasily A
authors.initials: VA
authors.lastname: Milyukov
authors.forename: Oleg G
authors.initials: OG
authors.lastname: Sinyashin