화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.117, No.28, 8547-8554, 2013
Charge-Transfer Electronic Absorption Spectra of 1-Ethylpyridinium Cation and Halogen Anion Pairs in Dichloromethane and as Neat Ionic Liquids
The charge-transfer (CT) absorption bands of ion pairs composed of 1-ethylpyridinium (Epy(+)) and halogen anions (X-: Cl, Br, or I) were measured in dichloromethane solutions of EpyX. The CT band of the Epy(+)I(-) ion pair shows clear splitting because of spin-orbit interaction in the excited state. The CT transition energy of an Epy(+)X(-) ion pair in a dichloromethane solution is related to electron affinity of X, which is in accordance with the Mulliken theory for CT bands. Extinction coefficients for the CT bands of the Epy(+)X(-) ion pairs in dichloromethane were determined using the measured absorbance, and the ion-pair concentration was estimated on the basis of electroconductivity. Structures of Epy(+)X(-) ion pairs were also evaluated on the basis of both quantum-chemical calculations and NMR spectroscopy. In addition, in the absorption spectrum measured for neat EpyI liquid, a broad band appeared at a longer wavelength side of the S-1(pi pi*) band. This new band has been assigned to the CT band of the Epy(+)I(-) ion pair formed in neat EpyI liquid.