Spectroscopic behavior of the alkali salts of noncyclic polyethers: Evidence for interaction between the end groups.
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The electronic and fluorescence spectra of the alkali salts of noncyclic polyethers exhibiting selective transport for the lithium ion were investigated. In the electronic spectra hypochromicity in CH<SUB>2</SUB>Cl<SUB>2</SUB> dependent on the kind of alkali metal ions was observed, and the magnitude of the hypochromic effect decreased in the following order: Li<SUP>+</SUP>>Na<SUP>+</SUP>>K<SUP>+</SUP>>Rb<SUP>+</SUP>>Cs<SUP>+</SUP>. Using the polar solvents, EtOH and MeCN, instead of nonpolar CH<SUB>2</SUB>Cl<SUB>2</SUB>, the hypochromicity is small. Also, in the fluorescence spectra, the quenching phenomenon dependent on the kind of alkali metal ions appeared in the same sequence as the hypochromicity in the electronic spectra. It is suggested that these results, together with our previous results, support a stacking structure between the terminal aromatic rings of the lithium salt in a nonpolar solvent, which has been proposed from the inspection of the CPK model building.
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