Ultra-fine Structure Control of Organic Crystals Using Solid-State Polymerization Reactions

在这个项目中，我们研究了不饱和有机化合物的拓扑化学聚合、二聚化、异构化以及所生成的聚合物晶体的相变和插层反应，揭示了控制有机固体材料的反应、结构和性能的固相反应机理。我们首先研究了反应过程中晶体结构的变化和晶体中菌株的积累，以揭示作为1，3-二烯单体的Muconic酯通过晶体到晶体的转化发生拓扑化学聚合、EZ-光异构化和[2+2]环二聚的机理。在原位X射线晶体结构分析的基础上，提出了各种不饱和有机化合物的晶格控制反应的固相反应机理。接下来，我们用固相聚合的方法合成了四种立体规则多酸盐，揭示了插层化合物的反应行为和层状结构。客体分子的取向受主体聚合物的规整性控制。我们制备了由结晶型有机聚合物和金属微粒组成的纳米复合材料。此外，我们还开发了一种以烷基胺和芘为客体的双插层方法来控制固态下的荧光性质。一种芳香族化合物被分别引入到铵聚合物晶体的疏水层中，并显示出来自单分子的荧光发射，而不是准分子。我们还发现了聚二乙炔在固体膜、聚合物基质和溶液中的热致变色性，其滞后环随温度的变化而变化。它们是由聚合物聚集体的形成和聚合物链的重组引起的。

In this project, we have investigated the topochemical polymerization, dimerization, isomerization of unsaturated organic compounds as well as the phase transition and the intercalation reactions of the resulting polymer crystals, and revealed solid-state reaction mechanisms for controlling the reactions, structures, and properties of organic solid materials. We first investigated a change in the crystal structures and the accumulation of a strain in the crystals during the reaction to reveal the mechanism of the topochemical polymerization, EZ-photoisomerization, and [2+2] cyclodimerization of muconic esters as the 1,3-diene monomers via a crystal-to-crystal transformation. We proposed a solid-state reaction mechanism for the crystal-lattice controlled reactions of various unsaturated organic compound based on the results of in situ X-ray crystal structure analysis during the polymerization. Next, we prepared four kinds of stereoregular polymuconates by solid-state polymerization and revealed the reaction behavior and the layered structure of intercalation compounds. The orientation of the guest molecules is controlled according to the host polymer tacticity. We have fabricated the nanocomposite consisting of a crystalline organic polymer and fine metal particles. 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. We also found the thermochromism of polydiacetylenes in a solid film, polymer matrix, and solutions with a hysteresis loop as a function of temperature. They are accounted for by the formation of polymer aggregates and reorganization of the polymer chains.