Synthesis and Evaluation of Functionality of Polymer Crystal Hybrid with Controlled Nanostructures

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In this project, we have investigated the topochemical polymerization of unsaturated organic compounds as well as the phase transition and intercalation of the resulting polymer crystals, and revealed solid-state reaction mechanism in order to control reactions, structures, and properties of organic solids. The organic intercalation system consisting of layered organic polymers and guest amines has some characteristics different from a large number of known intercalation compounds used as inorganic hosts. The polymer crystals as the organic intercalation host have the carboxylic acid orderly arranged along the polymer chains in a high density. The positional, conformational and orientation control of the guest molecules is possible by the host polymer structure, such as tacticity. First, we have report the polymerization reactivity of muconic esters as the 1,3-diene monomers during solid-state polymerization via a crystal-to-crystal transformation process. Single crystals structure ana … More lysis for monomers and the corresponding polymers revealed the solid-state polymerization kinetics closely related to a molecular stacking distance in the monomer crystals. Powder X-ray diffractions have revealed an intermediate change in the crystal structure during the polymerization by continuous X-ray irradiation. Next, w revealed the reaction behavior and the layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as the host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as infrared and Raman spectroscopies. We have found that the orientation of the guest molecules are controlled according to the host polymer tacticity, depending on the structure of the two-dimensional hydrogen bond network formed in the polymer sheets of the crystals. Furthermore, we developed a double-intercalation method using alkylamine and pyrene as the guests to control the fluorescence property in the solid state. An aromatic compound is separately introduced into the hydrophobic layers of the ammonium polymer crystals and shows a fluorescence emission from the single molecule, but not the excimer. This method can be applied to various organic photofunctional materials showing unique fluorescence properties. Thus, our organic polymer hosts are expected to be developed into new field of intercalation chemistry and material science. Less