Development of New Intramolecular Cyclization of Acetylenic Compounds for Materials Science

本研究的目的是开发新的炔属化合物环化反应，从而产生基本的和重要的新型π共轭骨架，并在此基础上开辟有机电子学的新领域。在本研究中，我们特别关注梯形π共轭结构，并探索新的合成方法。我们已经成功地开发了几种新的反应，并合成了一系列重要的π电子材料。主要成果如下：1.二炔的还原Bergman型环化：Bergman环化是二炔的热进行内-内模式环化的一个例子。我们现在已经成功地开发了这种环化的阴离子形式，即，使用环状邻-双（甲硅烷基乙炔基）苯作为起始原料的内-内模式还原环化。该反应对功能化并苯的合成具有重要意义。 关于我们 第2条。硅/碳桥低聚（对苯撑乙烯基）：在二苯乙炔衍生物分子内还原双环化的基础上，我们成功地合成了一系列硅茚衍生物和硅/碳桥低聚（对苯撑乙烯基）。详细研究了它们的电子物理性质，揭示了硅原子对激发态动力学的影响.基于新发展的级联阴离子环化反应和一锅法分子内还原环化反应，分别合成了硅/硫桥连的二苯乙烯基苯和15族元素桥连的二苯乙烯，这两种化合物均具有独特的荧光性质.扩展的杂并苯：我们开发了一种新的分子内三环化的二炔化合物与硫产生稠合的1，2-二噻英。该方法与脱卤作用的组合产生一系列稠合的低聚噻吩。研究了它们的物理化学和电化学性质，以显示它们作为有机电子材料的潜力，如有机晶体管。少

The objective of this research was to develop new cyclization reactions of acetylenic compounds, which produce fundamental and important novel π-conjugated frameworks, and to open a new aspect in the organic electronics on the basis of this synthetic study. In this research, we particularly focus our attention on the ladder-type π-conjugated structures, and explored new synthetic methodologies for them. We have succeeded in the developments of several types of new reactions and have synthesized a series of important π-electron materials. Our achievements are summarized as follows.1. Reductive Bergman-type cyclization of diynes : Bergman cyclization is an example of the thermally-proceeding endo-endo mode cyclization of diynes. We have now succeeded in the development of an anionic version of this cyclization, i.e., endo-endo mode reductive cyclization using cyclic o-bis (silylethynyl) benzenes as the starting materials. This reaction will be useful for the functionalized acene synthesi … More s.2. Silicon/carbon-bridged oligo(p-phenylenevinylene)s : On the basis of an intramolecular reductive double cyclization of diphenylacetylene derivatives, we have succeeded in synthesizing a series of silaindene derivatives and silicon/carbon-bridged oligo(p-phenylenevinylene)s. The detailed study in their photophysical properties has revealed the effect of the silicon atoms on the excited state dynamics.3. Oligo(p-phenylenevinylene)s containing various main group elements : Silicon/sulfur-bridged distyrylbenzenes and group 15 element-bridged stilbenes have been synthesized based on the newly developed cascade-type anionic cyclization and one-pot intramolecular reductive cyclization, respectively, both of which shows unique fluorescence properties.4. Extended heteroacenes : We have developed a new intramolecular triple cyclization of diacetylenic compounds with sulfur to produce fused 1,2-dithiins. Combination of this methodology with the dechalcogenation produces a series of fused oligothiophenes. Their photophysical and electrochemical properties have been investigated to show their potentials as the materials for organic electronics, such as organic transistors. Less