Thermal behavior of J-aggregates in mixed Langmuir-Blodgett films composed of merocyanine dye and deuterated arachidic acid investigated by UV-visible and infrared absorption spectroscopy.
We have investigated the thermal behavior of J-aggregates in the mixed Langmuir-Blodgett (LB) films composed of the merocyanine dye (MS18)-deuterated arachidic acid (C20-d) binary system in the temperature range from 25 to 250 degrees C by means of UV-visible and IR transmission absorption spectroscopy. The temperature-dependent variations in both UV-visible and IR absorption spectra indicate that the MS18 aggregation states are linked with the MS18 intramolecular charge transfer and the behavior of the packing, orientation, conformation, and thermal mobility of the MS18 hydrocarbon chain. The J-aggregate formed at 25 degrees C in the mixed LB films dissociates in the temperature range from 25 to 110 degrees C, which is mainly ascribed to the increase in the thermal mobility of MS18 hydrocarbon chain and the dissociation of the chelation by a cadmium ion to the MS18 keto group. A thermally induced blue-shifted band appears at around 515 nm from 110 to 160 degrees C. This band is attributed to oligomeric aggregation with side-by-side alignment of the MS18 transition dipole moments on the basis of the shift to a higher-energy side, broadening, and temporary increment of the MS18 intramolecular charge transfer of the band. Consequently, the appearance of the thermally induced blue-shifted band indicates the possibility that the MS18 aggregation states can be controlled from the red shift to the blue shift by the annealing method adopted in the present study.
Hirano
Yoshiaki
Y
Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan.
Tateno
Shinsuke
S
Ozaki
Yukihiro
Y