Direct Observation of Alkali Metal Ion Recognition Processes at the Heptane/Water Interface by Second Harmonic Generation Spectroscopy

Abstract

Alkali metal ion recognition with [2-hydroxy-5-(4-nitrophenylazo)phenyl]-methyl-15-crown-5 (azoprobe 1) at the heptane/water interface was investigated by in situ second harmonic generation (SHG) spectroscopy. Upon addition of alkali metal ions, the second harmonic (SH) intensity of azoprobe 1 at the heptane/water interface was found to increase selectively. The observed selectivity of K+ > Na+ > Li+ > TMA+ was essentially the same order as that of the extractability for alkali metal ions in the 1,2-dichloroethane/water extraction. Although the Li+ extractability by azoprobe 1 was very low in the 1,2-dichloroethane/water system, the observed increase of SH intensity suggested that the Li+ complex could distribute to some extent at the heptane/water interface. The red shift of the SHG spectra for azoprobe 1 revealed that the heptane/water interface had an intermediate polarity between those of the two solvents. The light polarization analysis of the SH intensity exhibited a clear orientation change of azop...