Development of New Intramolecular Cyclization of Acetylenic Compounds for Materials Science

本研究的目的是开发新的乙炔类化合物的环化反应，生成基础的和重要的新型π共轭框架，并在此基础上开辟有机电子学的新领域。在本研究中，我们特别关注了阶梯型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反应，并合成了一系列重要的π电子材料。我们的成就总结如下。双炔的还原性Bergman型环化：Bergman环化是双炔热过程的内端-内端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版本，即使用环o-双（硅乙基）苯作为起始材料的内-内模式还原环化。该反应可用于功能化丙烯腈的合成。硅/碳桥低聚物（对苯基乙烯）s：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烯衍生物和硅/碳桥低聚物（对苯基乙烯）s。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。3 .基于新发展的级联式阴离子环化和一锅分子内还原环化，分别合成了含有多种主族元素的低聚（对苯基乙烯）：硅/硫桥式二苯基苯和15族元素桥式二苯基苯，两者都具有独特的荧光性质。扩展杂杂烯：我们开发了一种新的分子内二乙基化合物与硫的三环化反应，以产生融合的1,2-二硫胺。这种方法与脱硫反应相结合，产生一系列熔融的低硫噻吩。研究了它们的光物理和电化学性能，显示了它们作为有机电子材料（如有机晶体管）的潜力。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