Experimental and Computational Studies of Nuclear Substituted 1,1'-Dimethyl-2,2'-Bipyridinium Tetrafluoroborates

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• 作者：Dong Zhang ; Joã ; o P. Telo ; Chen Liao ; Sean E. Hightower ; Edward L. Clennan
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：December 27, 2007
• 年：2007
• 卷：111
• 期：51
• 页码：13567 - 13574
• 全文大小：300K
• 年卷期：v.111,no.51(December 27, 2007)
• ISSN：1520-5215

文摘

The synthesis and spectral properties of a new 2,2'-bipyridinium ion, 1,1'-dimethyl-4,4'-(dimethylamino)-2,2'-bipyridinium bis(tetrafluoroborate) are reported. Rotation of the dimethylamino group is slow at roomtemperature on the 400 MHz ¹H and 100 MHz ¹³C NMR time scales. Complete line shape fit of the dynamicallybroadened NMR spectra was used to determine the activation barriers for this process. The first complete setof UV-vis spectra for a 2,2'-bipyridinium dication and its one- and two-electron reduced products was reported.TD-DFT calculations were used to help assign the origin of the long wavelength absorptions in these species.The effect of substituents on the energies and conformational potential energy surfaces of all three specieswere also examined using the B3LYP/6-31G(d) computational method.