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Synthesis of Panchromatic Ru(II) Thienyl-Dipyrrin Complexes and Evaluation of Their Light-Harvesting Capacityстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Li G., Ray L., Glass E.N., Kovnir K., Khoroshutin A., Gorelsky S.I., Shatruk M.
- Журнал: Inorganic Chemistry
- Том: 51
- Номер: 3
- Год издания: 2012
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 1614
- Последняя страница: 1624
- DOI: 10.1021/ic2019204
- Аннотация: Ru(II) complexes with 5-(3-thienyl)-4,6-dipyrrin (3-TDP), containing 2,2?-bipyridine (bpy) or 4,4?-bis(methoxycarbonyl)-2,2?-bipyridine (dcmb) as coligands, have been prepared and extensively characterized. Crystal structure determination of [Ru(bpy)2(3-TDP)]PF6 (1a) and [Ru(bpy)(3-TDP)2] (2) reveals that the 3-thienyl substituent is rotated with respect to the plane of the dipyrrinato moiety. These complexes, as well as [Ru(dcmb)2(3-TDP)]PF6 (1b), act as panchromatic light absorbers in the visible range, with two strong absorption bands observable in each case. A comparison to known Ru(II) complexes and quantum-chemical calculations at the density functional theory (DFT) level indicate that the lower-energy band is due to metal-to-ligand charge transfer (MLCT) excitation, although the frontier occupied metal-based molecular orbitals (MOs) contain significant contributions from the 3-TDP moiety. The higher energy band is assigned to the Ï€?Ï€* transition of the 3-TDP ligand. Each complex exhibits an easily accessible one-electron oxidation. According to DFT calculations and spectroelectrochemical experiments, the first oxidation takes place at the RuII center in 1a, but is shifted to the 3-TDP ligand in 1b. An analysis of MO energy diagrams suggests that complex 1b has potential to be used for light harvesting in the dye-sensitized (Grätzel) solar cell.
- Добавил в систему: Хорошутин Андрей Васильевич