Pressure and solvent shifts of absorption spectra. II. Intramolecular charge transfer bands.
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概要
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Absorption spectra of intramolecular CT bands of nitrobenzene, <I>p</I>-nitrophenol, <I>p</I>-nitroaniline, acetophenone, <I>p</I>-hydroxyacetophenone, and <I>p</I>-aminoacetophenone are observed in several nonpolar solvents at 1 bar, and in heptane up to 4400 bar. The fact that all solvent shifts are linearly red for the function of refractive index (<I>n</I>) of solvents, (<I>n</I><SUP>2</SUP>−1)/(2<I>n</I><SUP>2</SUP>+1), consists with the solvent shift theory. On the other hand, the pressure shifts are not straight but convex upward for (<I>n</I><SUP>2</SUP>−1)/(2<I>n</I><SUP>2</SUP>+1) and the red shifts by pressure exceeds the solvent shifts. The similar convex pressure shifts are found in <SUP>1</SUP>L<SUB>b</SUB> bands of several aromatic compounds by plotting the high pressure data of Robertson <I>et al.</I> in spite of the straight solvent shifts in these <SUP>1</SUP>L<SUB>b</SUB> bands measured by us. Therefore the convex pressure shift may be regarded as a general tendency of the electronic spectrum, being ascribed to decrease in the distance between a solute and the surrounding solvents by compression. From comparison with the pressure shift of the intramolecular CT band, it is suggested that, in the pressure shift of the intermolecular CT band of the I<SUB>2</SUB> complexes shifted to red previously, the effect of decrease in the bond distance between a donor and an acceptor proposed by Offen and Nakashima contributes to not a red shift but a blue shift.
- 公益社団法人 日本化学会の論文
著者
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Sawamura Seiji
Department Of Chemistry Faculty Of Science And Engineering Ritsumeikan University
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Suzuki Keizo
Department Of Chemistry Faculty Of Science And Engineering Ritumeikan University
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Taniguchi Yoshihiro
Department Of Applied Chemistry Faculty Of Science And Engineering Ritsumeikan University
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