The Role of πσ* State in Intramolecular Charge Transfer of 4-(DIMETHYLAMINO){-}BENZONITRILE and Related Molecules

Details The Role of πσ* State in Intramolecular Charge Transfer of 4-(DIMETHYLAMINO){-}BENZONITRILE and Related Molecules The Role of πσ* State in Intramolecular Charge Transfer of 4-(DIMETHYLAMINO){-}BENZONITRILE and Related Molecules

Jun 2011

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..confetg11f&link_type=abstract

"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec

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The solvent-polarity dependence and temporal characteristics of the transient absorption of 4-(dimethylamino)-benzonitrile, DMABN, and 4-(dimethylamino)benzethyne, DMABE, demonstrate the presence of the πσ*-state absorption at about 700 nm and the ππ* (LE)-state absorption at about 520 nm and 450 nm. The rise and decay times of the πσ*-state transient differ from those of the ππ*-state transients in both compounds. Moreover, the peak position of the πσ*-state absorption is blue-shifted and more intense in acetonitrile as compared to n-hexane, whereas the band positions of the ππ*-state absorptions are essentially the same in the two solvents. For DMABN in acetonitrile, the rise time (˜ 4.3 ps) of the twisted intramolecular charge transfer (TICT)-state transient at 330 nm is identical to the decay time of the πσ*-state transient. The 4.8 ns decay time of the TICT-state absorption of DMABN is longer than the 2.9 ns decay time of the intramolecular charge-transfer (ICT) fluorescence, indicating that the fluorescent ICT state differs from the TICT state observed in transient absorption. These results are consistent with the presence of a low-lying πσ* state in DMABN (and DMABE), and the role the πσ* state plays in the formation of the TICT state of DMABN.

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