Electronic Structures and Absorption Spectra of Linkage Isomers of Trithiocyanato (4,4',4' '-Tricarboxy-2,2':6,2' '-terpyridine) Ruthenium(II) Complexes: A DFT Study
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- 作者：Sutapa Ghosh ; G. Krishna Chaitanya ; K. Bhanuprakash ; Md. K. Nazeeruddin ; M. Grä ; tzel ; P. Yella Reddy
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：September 18, 2006
- 年：2006
- 卷：45
- 期：19
- 页码：7600 - 7611
- 全文大小：472K
- 年卷期：v.45,no.19(September 18, 2006)
- ISSN：1520-510X
文摘
Black dye (BD), isomer 1 ([RuII(H3-tctpy)(NCS)3]-1, where H3-tctpy = 4,4',4' '-tricarboxy-2,2':6,2' '-terpyridine) isknown to be an excellent sensitizer for dye-sensitized solar cells and exhibits a very good near-IR photo response,compared to other ruthenium dyes. Because isothiocyanate is a linear ambidentate ligand, BD has three otherlinkage isomers, [Ru(H3-tctpy)(NCS)2(SCN)]-1, isomer 2 and 2', and [Ru(H3-tctpy))(SCN)3]-1, isomer 3. In thisstudy, we have calculated the geometry of BD and its isomers by DFT. Further, we have analyzed the bonding inthese isomers using NBO methods. TDDFT calculations combined with scalar relativistic zero-order regularapproximations (SR-ZORA) have been carried out to simulate the absorption spectra. Calculations have beenperformed for the isomers both in vacuo and in solvent (ethanol). The inclusion of the solvent is found to beimportant to obtain spectra in good agreement with the experiment. The first absorption bands are dominated bythe metal-to-ligand charge transfer (MLCT) and ligand-to-ligand charge transfer (LLCT).