Experimental and Computational Studies of Nuclear Substituted 1,1‘-Dimethyl-2,2‘-Bipyridinium Tetrafluoroborates
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 room temperature on the 400 MHz 1H and 100 MHz 13C NMR time scales. Complete line shape fit o...
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Published in | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 51; pp. 13567 - 13574 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
27.12.2007
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Online Access | Get full text |
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Summary: | 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 room temperature on the 400 MHz 1H and 100 MHz 13C NMR time scales. Complete line shape fit of the dynamically broadened NMR spectra was used to determine the activation barriers for this process. The first complete set of 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 species were also examined using the B3LYP/6-31G(d) computational method. |
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Bibliography: | istex:CF6FB8277D4092735EB3E80C61361B550A218396 ark:/67375/TPS-WGQRLM18-H ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp074323u |