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
详细信息 查看全文
- 作者：Elena E. Zvereva ; Stefan Grimme ; Sergey A. Katsyuba ; Timur I. Burganov ; Almaz A. Zagidullin ; Vasily A. Milyukov ; Oleg G. Sinyashin
- 刊名：The Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：August 8, 2013
- 年：2013
- 卷：117
- 期：31
- 页码：6827-6834
- 全文大小：576K
- 年卷期：v.117,no.31(August 8, 2013)
- ISSN：1520-5215
文摘
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鈥揕UMO 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鈭捪€ 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.