Synthesis of Organic Functionality Materials by Use of Trithio-Cyclopropenium Ion

迄今为止，主要的兴趣是对环丙烯正离子、环丙烯酮和环丙烯硫酮这类最小的成环芳香体系的电子结构和物理性质等进行理论研究。另一方面，本研究主要致力于发展高应变三元开环的高<pi>电子化合物的独特反应，进而合成<pi>具有新物理性质和功能的新型高电子体系。在研究过程中，发现了以下两种反应。(1)在三丁基膦催化剂存在下，双（羟基苯基）环丙烯硫酮发生二聚反应，得到具有氧化还原活性的四（羟基苯基）噻吩并[3，2-B]噻吩，它与其二电子和四电子氧化配偶体构成了稳定而清晰的三色有机电致变色体系.（2）极性很强的二氰基二硫代和二苯基杯烯与二氨基富烯反应，得到了新型的（π）电子体系：二氨基奥富烯和醌型并环戊二烯，其中二氨基奥富烯对基态的极性结构贡献很大，有望成为一种很有前途的非线性光电子器件，并在杯烯化学方面取得了很大进展。通过核磁共振、X射线结构分析和分子轨道计算，确定了它们的电子结构。

Main interest has so far been directed toward theoretical investigation of electronic structures and physical properties etc. of cyclopropenium ion, cyclopropenone, and cyclopropenethione, samllest membered-ring aromatic systems. On theother hand, this research project was largely concerned in developing upique reactions due to a highly-strained three-membered ring opening of the above <pi>-electron compounds and furthermore in synthesizing new types of <pi>-electron systems with novel physicla properties and functions. During this research period the following two reactions were found out. (1) In the presenceof a tri-n-butylphosphine catalyst, bis(hydroxyphenyl) cyclopropenethione was subjected to dimerization, and a redox-active tetrakis(hydroxyphenyl)thieno[3,2-b]thiophene was obtained, which constructs a stable and distinct three-color organic electrochromic system with its two- and four-electron oxidized partner. (2)Very polarized dicyano-dithio- and -diphenyl calicenes reacted with diaminofulvene to afford new types of (pi)-electron systems, diaminoazulenofulvene and quinoid-type pentalene, of which the former compound has a large contributionof the polar structure in the ground state, thus giving much expectation as a promising component for non-linear optoelectronics.The present research also made a large progress in calicene chemistry. Thus,cyclic n-calicenes were synthesized, and their electronic structures were elucidated by the results of NMR, X-ray structural analysis, and MO calculations.