Spectroscopy and quantum-chemical calculations of nitro-bis-bipyridyl complexes of ruthenium(II) with 4-substituted pyridine ligands
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- 作者：K. I. Reshetova ; I. V. Krauklis ; S. V. Litke ; A. Yu. Ershov…
- 刊名：Optics and Spectroscopy
- 出版年：2016
- 出版时间：April 2016
- 年：2016
- 卷：120
- 期：4
- 页码：566-574
- 全文大小：805 KB
- 刊物类别：Physics and Astronomy
- 刊物主题：Physics
Optical Spectroscopy and Ultrafast Optics
Russian Library of Science - 出版者：MAIK Nauka/Interperiodica distributed exclusively by Springer Science+Business Media LLC.
- ISSN：1562-6911
- 卷排序：120
文摘
The luminescence, absorption, and luminescence excitation spectra of complexes cis-[Ru(bpy)2(L)(NO2)]+ [bpy = 2,2′-bipyridyl, L = pyridine, 4-aminopyridine, 4-dimethylaminopyridine, 4-picoline, isonicotinamide, or 4,4′-bipyridyl] in alcoholic (4 : 1 EtOH–MeOH) solutions are studied at 77 K. A linear correlation is established between the energy of the lowest electronically excited metal-toligand charge transfer state dπ(Ru) → π*(bpy) of the complexes and the pKa parameter of the free 4-substituted pyridines used as ligands L. The B3LYP/[6-31G(d)+LanL2DZ(Ru)] hybrid density functional method is used to optimize the geometry of complexes and calculate their electronic structure and the charge distribution on the atoms of the nearest environment of ruthenium(II) ions. It is shown that there exists a mutually unambiguous correspondence between the charge on the nitrogen atom of ligands L coordinated in the complex and the pKa parameter of ligands. The calculated energies of the electronically excited metal-to-ligand charge transfer states of complexes linearly (correlation coefficient 0.99) depend on the charge on the nitrogen atom of ligands L, which completely agrees with the experimental data.Original Russian Text © K.I. Reshetova, I.V. Krauklis, S.V. Litke, A.Yu. Ershov, Yu.V. Chizhov, 2016, published in Optika i Spektroskopiya, 2016, Vol. 120, No. 4, pp. 596–604.