Experimental and DFT studies on the DNA-binding trend and spectral properties of complexes [Ru(bpy)2L]2+ (L=dmdpq, dpq, and dcdpq)
| Autor: | Liang N. Ji, Jun Li, Xue W. Liu, Hong Deng, Zong W. Mao, Kang C. Zheng |
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| Rok vydání: | 2005 |
| Předmět: |
Ligand
Intercalation (chemistry) Substituent Frontier molecular orbital theory Time-dependent density functional theory Affinities Inorganic Chemistry Crystallography chemistry.chemical_compound Quinoxaline chemistry Computational chemistry Materials Chemistry Density functional theory Physical and Theoretical Chemistry |
| Zdroj: | Inorganica Chimica Acta. 358:3311-3319 |
| ISSN: | 0020-1693 |
| Popis: | The trend in DNA-binding affinities and the spectral properties of a series of Ru(II) polypyridyl complexes, [Ru(bpy) 2 (dmdpq)] 2+ ( 1 ), [Ru(bpy) 2 (dpq)] 2+ ( 2 ), [Ru(bpy) 2 (cndpq)] 2+ ( 3 ) (bpy = 2,2′-bipyridine; dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline; dmdpq = di-methyl-dpq; dcdpq = di-cyano-dpq), have been experimentally and theoretically investigated. The DNA-binding constants K b of the complexes were determined systematically with spectrophotometric titration. The density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were carried out for these complexes. The experimental results show that these complexes bind to DNA in intercalation mode, and the order of their intrinsic DNA-binding constants K b is K b ( 1 ) K b ( 2 ) ≪ K b ( 3 ). The substituents on the intercalative ligands of the complexes play a very important role in the control of DNA-binding affinities of the complexes, in particular, the stronger electron-withdrawing substituent (–CN) on the intercalative ligand can greatly improve the DNA-binding property of the derivative complex. The trend in DNA-binding affinities as well as the spectral properties of metal–ligand charge-transition ( 1 MLCT) of this series of complexes can be reasonably explained by applying the DFT and TDDFT calculations and the frontier molecular orbital theory. |
| Databáze: | OpenAIRE |
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