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Excited states of 4-dimethylaminopyridines: magnetic circular dichroism and computational studies.

The ultraviolet transitions of 4-(dimethylamino)pyridine and its derivatives: 3-methyl-4-(dimethylamino)pyridine and 3,5-dimethyl-4-(dimethylamino)pyridine were investigated by electronic absorption and magnetic circular dichroism (MCD) spectroscopy, and by quantum chemical calculations. The ortho-methylation in the pyridine ring creates a steric hindrance to coplanarity. The resulting changes in the strength of the dimethylamino substitutent are reflected in the MCD spectra. Near-UV experimental data indicate a presence of three low-energy transitions, assigned to 1Lb, 1La and 1(n,pi*) excited states. These results are corroborated by TD-DFT and INDO/S calculations.[1]

References

  1. Excited states of 4-dimethylaminopyridines: magnetic circular dichroism and computational studies. Szydłowska, I., Kyrychenko, A., Gorski, A., Waluk, J., Herbich, J. Photochem. Photobiol. Sci. (2003) [Pubmed]
 
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