• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.833-836
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• 2001

Infrared absorption spectra of $\alpha\omega-diphenylpolyenyl$, anions Ph(CH)nPh- (DPn-, n=7, 9, and 13) in the tetrahydrofuran-d6 solutions was measured in the range of 1700 and 1200 cm-1 . The infrared spectra obtained from anions (DPn) showed considerable difference from their neutral species (DPn); their intensities were enhanced at least two orders of magnitude stronger than their neutral species. The in-plane CH bending modes at 1464 and 1375 cm-1 are correspondingly strengthened with the chain length increased, but the C=C stretching at 1541 cm-1 is weakened and frequencies are not changed. We provide an IR evidence for the first time that the bond order or bond alternations of the anions (soliton) are different from those of radical anions (polaron) as well as neutral species.

• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.837-841
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• 2001

The electronic absorption and Raman spectra of $\alpha\omega-diphenylpolyenyl$, anions Ph(CH)nPh- (DPn- , n = 3, 5, 7, 9, and 13), with odd number of carbons at the polyene part, have been studied in the tetrahydrofuran (THF) solutions and in their solid film states, respectively. In the case of Raman spectra for DPn- , the frequencies and relative intensities of some Raman peaks regularly change with the increase of polyene chain length. The spectral patterns of anions (DPn- ) are very similar with those of radical anion (DPn${\cdot}$- ). However, the C=C stretching peaks of DPn- anions are observed in the 25-35 cm-1 higher frequency region than those of DPn${\cdot}$- radical anions. In the case of long chain models such as DP9- and DP13- , the C=C stretching peaks are observed in even higher frequency region than those of the corresponding neutral polyenes such as DP8, DP10, and DP12. The Raman patterns of DPn- anions in the THF solutions are similar with those in their solid film states. On the other hand, their electronic absorption spectra show a considerable difference each other. The n- ${\pi}*$ electronic absorption bands of DPn- anions in the THF solutions have been observed in the 0.27-0.39 eV lower energy region than those in their solid film states due to the solvent effects on polyene anions.