Conformationally flexible molecules of diethyl p-phenylenediacrylate (1) and methyl 4-(β-methoxycarbonylvinyl)-α-cyanocinnamate (2) exhibit excimer emission in concentrated solutions. The excimer of 1 is formed via excitation of the ground state aggregates of 1. In crystalline state, only 2, which has the crystal structure of B-type in Stevens’ classification, being different from the crystal structure (A-type) of 1, gives excimer emission. The stack-type structure is proposed for the excimers of 1 and 2.
The photopolymerization behavior of p‐phenylene diacrylic acid dimethyl ester (p‐PDA Me) crystal and the thermal behavior of the resultant poly‐p‐PDA Me were investigated. From the kinetic study of polymerization at various temperatures a topochemical process via a stepwise mechanism was observed. Continuous change from monomer to polymer crystals was demonstrated by x‐ray diffraction pattern and DSC analysis. Crystallinity of the reacting phase was maintained at an extremely high degree during the polymerization process in support of monomer crystal lattice control. Thermal study on as‐polymerized poly‐p‐PDA Me crystal confirmed that the thermal reaction was a polymer crystal lattice‐controlled depolymerization, which was followed by miscellaneous processes that involved vaporization, sublimation, and deterioration of the oligomeric or monomeric units of p‐PDA Me. Thermal stability was dependent on the molecular weight. All the results are compared with those of four‐center‐type photopolymerization in the crystalline state.
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