Influence of monolayer state on spectroscopy and photoisomerization of an amphiphilic styryl-pyridinium dye on a solid substrate

The spectroscopy and photochromic properties of transferred monolayers of the amphiphilic styryl-pyridinium dye 4-(3',4'-dimethoxystyryl)-N-octadecylpyridinium perchlorate (DMPOP) were studied at different conditions during their transfer. The emission maxima of the monolayers transferred from the air-water interface in the liquid-expanded phase are strongly dependent on the surface pressure applied during the transfer process, even at values when the area per molecule is 2-3 times larger than the area occupied by a chromophore. In monolayers transferred from the liquid-condensed phase, the presence of a different kind of aggregates was observed. The fluorescence emission properties of the monolayers can be reversibly modulated by photoinduced E-Z isomerization. A blue shift up to 72 nm in the emission maximum, depending on the transfer conditions of the films, can be obtained by irradiation with blue light, and partially recovered (a red shift of up to 26 nm) with UV radiation. The rate at which the first process (E -> Z) takes place is drastically reduced in monolayers transferred from the liquid-condensed phase as compared to those transferred from the liquid-expanded one. However, the rate of the reverse reaction (Z -> E) is not significantly altered. These properties make DMPOP a promising material for the preparation of Langmuir-Blodgett films, whose properties can be effectively controlled by the transfer conditions and subsequently optically modulated, for potential applications as photonics devices for data storage.