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| - Formation and Photodissociation of a Jet-Cooled Intramolecular Exciplex in theBichromophoric EDA System: Multiconformations and Deuteration Effect
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| - The intramolecular exciplex formation and photodissociation in asupersonic free jet have been studied fordeuterated anthryl bichromophoric EDA systems1-(9-anthryl-d8)-3-(m-(N,N-dimethylamino)phenyl)propanes(9-An-d-m-DMA) in comparison with thecorresponding undeuterated compounds (9-An-m-DMA).Fluorescence hole burning depletion spectra in the anthryl deuterated9-An-d-m-DMA suggests the presenceoftwo distinct isomeric conformers. The S1 vibrationalenergy thresholds for the exciplex formation in the twoisomeric forms of the deuterated compounds are considerably smallerthan those of the respective undeuteratedcompounds. The photodissociation of the exciplex leading to theformation of the excited-state anthryl moietywas observed in the excitation of the transient absorption band of thejet-cooled exciplex (Sn−S1).Thedecay time of the photodissociation-induced anthryl fluorescence isshorter for 9-An-d-m-DMA than for9-An-m-DMA. These deuteration effects of the anthryl moietyon the formation and photodissociation of the exciplexmay be attributed to the role of the vibrational level density of theanthryl moiety in these excited-statereaction dynamics. The shorter decay time of thephotodissociation-induced anthryl fluorescence of 9-An-d-m-DMA relative to 9-An-m-DMA isconsistent with the conclusion that the emission originates fromthevibrationally highly excited S1 anthrylmoiety.
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