Development of New Intramolecular Cyclization of Acetylenic Compounds for Materials Science

本研究的目的是开发新的烯烃类化合物的环化反应，从而产生基础和重要的新型π共轭骨架，并在此合成研究的基础上开辟有机电子学的新领域。在这项研究中，我们特别关注梯形π共轭结构，并探索了新的合成方法。我们已经成功地开发了几种新的反应类型，并合成了一系列重要的π电子材料。我们取得的成果概括如下：1.二炔类化合物的还原Bergman型环化反应：Bergman环化反应是二炔类化合物热过程内切-内切模式环化反应的一个例子。我们现在已经成功地开发了这种环化反应的阴离子版本，即以环O-二(硅乙炔)苯为起始原料的内内式还原环化反应。该反应可用于功能化的并苯合成…更多的S2。硅/碳桥联低聚对苯乙炔S：在二苯乙炔衍生物分子内还原双环的基础上，我们成功地合成了一系列硅杂烯衍生物和硅/碳桥联低聚对苯乙炔S，通过对其光物理性质的详细研究，揭示了硅原子对激发态动力学的影响。基于最新发展的级联阴离子环化反应和一锅分子内还原环化反应，合成了具有多种主族元素：硅/硫桥联的二苯基二苯醚和15族元素桥联的二苯乙烯类低聚对苯乙叉S，两者均具有独特的荧光性质。扩展杂烯：我们开发了一种新的双乙炔化合物与硫的分子内三环反应，以生成稠合的1，2-二硫杂环化合物。将这种方法与脱氢反应相结合，可以得到一系列融合的低聚硫吩类化合物。研究了它们的光物理和电化学性质，展示了它们作为有机电子材料的潜力，如有机晶体管。较少

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