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• W2083687777 abstract "The anomalous fluorescence of solutions of 4-(dimethylamino)benzonitrile (DMABN) and 4-(dimethylamino)benzonitrile (DEABN) in benzene and toluene is shown to originate from exciplexes, formed by DMABN or DEABN and the aromatic solvent. The fluorescence spectra of DMABN and DEABN in an alkane containing a varying amount of the aromatic solvent, are decomposed into the normal and the anomalous fluorescence band, FN and FE, according to a new procedure. This decomposition shows that 1:1 as well as 1:2 exciplexes, consisting of one 4-(dialkylamino)benzonitrile molecule and one or two molecules of the aromatic solvent, respectively, account for the anomalous fluorescence at 295 K. At 193 K only the 1:1 exciplexes are present. The decomposition also yields the shifts of both FN and FE as a function of the dielectric properties of the solvent, which leads to an estimation of the electric dipole moments of the excited, bare molecules DMABN or DEABN and their 1:1 exciplexes. This estimation improves if the effect of the polarizability of the solute is taken into account. After this correction the electric dipole moment of DMABN and DEABN in their first excited single states is determined to be 10±2 and 12±2 D, respectively. The dipole moment of the DMABN—benzene and DMABN—toluene exciplexes are both equal to 17±4 D, whereas the dipole moments of the DEABN—benzene and DEABN—toluene exciplexes are measured to be 22±5 and 21±5 D, respectively. Grounds for a sandwich-like exciplex configuration are provided. The change in entropy, ΔS, accompanying the 1:1 exciplex formation, as well as the 1:1 exciplex stabilization energy, ΔH, are derived from the time dependence of the fluorescence as a function of both temperature and the concentration of the aromatic solvent. The results indicate that the 1:1 exciplex formation corresponds with an exothermic reaction with an unfavourable entropy factor for both DMABN and DEABN. The nature of the exciplexes is discussed." @default.
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• W2083687777 date "1993-08-01" @default.
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• W2083687777 title "On the source of the anomalous fluorescence of 4-(dialkylamino)benzonitrile in aromatic hydrocarbon solvents: the role of exciplexes" @default.
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• W2083687777 doi "https://doi.org/10.1016/0301-0104(93)80009-x" @default.
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