Morphology and thermochromic phase transition of merocyanine J-aggregate monolayers at the air–water and solid–water interfaces

Thermal changes of the merocyanine dye (MD) monolayer at the air–water interface were investigated under various subphase conditions in order to elucidate the formation mechanism and to control morphological and chromatic properties of two-dimensional MD J-aggregate crystallites (JC) formed in the monolayer. The dissociation temperature (Td) of the JC to the monomer MD was measured for different counterions of MD molecules in the subphase. The JC size was found to be dependent on the subphase temperature; it becomes larger when the JC is formed at a temperature closer to Td. This phenomenon is qualitatively reproduced by the numerical simulation of the Cahn–Hilliard equation. In the case of the MD monolayer on the subphase which contains two kinds of counterions, it exhibits a reversible thermochromic transition between two different JC states. The chromatic change is discrete, and is attributed to the structural phase transition of the JC induced by the mutual recombination of two kinds of counterions to MD molecules. The structural difference between the high and low temperature JC states is examined by the point dipole model. The transition temperature and thermal hysteresis width can be varied by the fraction of 2 counterions. In situ observations using a multipurpose nonlinear optical microscope revealed that the transition is of first order and the nucleation and growth process of the low temperature phase in the high temperature matrix was observed. The JC size of the low temperature phase became much larger through the recrystallization process. For future application of this phenomenon, an airtight cell consisting of two monolayers at the solid–water interface and the subphase was developed. In the cell, the same reversible transition occurs, but with a slow relaxation.