Synthesis and Properties of Novel pi-Electronic Hydrocarbons Having sigma-pi Interaction

1.含双环辛烯骨架的环戊二烯基PI-体系的合成以双环[2.2.2]辛烯(简称BCO)为结构单元，合成了具有新性质的PI-体系。因此，我们合成了一系列带有两个BCO单元的取代环戊二烯衍生物，并对它们的氧化还原行为进行了详细的研究。2.含BCO单元的硅烷和大环戊二烯的合成。根据UV数据和分子轨道计算结果，研究了Sigma-pi相互作用的存在。3.生成了与两个BCO基团相连的苯乙炔，并通过捕获实验证实了上述苯乙炔的生成。4.苯并二聚体与四个BCO基团发生双Diels-Alder反应合成了四个BCO基团的菲衍生物，并对其进行了双Diels-Alder反应，合成了上述四个苯并二聚体的双Diels-Alder衍生物。通过使用电化学和有机化学氧化还原反应，证明了由于sigma-pi相互作用而引起的HOMO水平的显著增加。由该菲衍生物成功地生成了稳定的阳离子自由基和阳离子。

1.Synthesis of the Cyclopentadienylpi-System Annelated with Bicyclooctene Frameworks.Bicyclo [2.2.2] octene (abbreviated as BCO) was used as the structural unit for the synthesis of pi-systems having novel properties. Thus, a series of substituted cyclopentadienyl derivatives annelated with two BCO units have been synthesized and their redox behaviors investigated in detail.2.Synthesis of Sila-and Germacyclopentadienes Annelated with BCO Units.The above silole and germole derivatives have been newly synthesized and their spectral properties fully characterized. The presence of sigma-pi interaction has been investigated based on the results of UV data and MO calculations.3.Generation of the Benzyne Annelated with Two BCO Units.The generation of the above mentioned benzyne has been confirmed by trapping experiment. This benzyne has also been converted to the biphenylene derivative and its unique redox behaviors were clarified.4.Synthesis and Properties of the Anthracene Annelated with Four BCO Units.The above mentioned anthracene derivative has been newly synthesized by the use of double Diels- Alder reaction of the BCO dimer with p-benzoquinone as a dienophile. The notable increase in HOMO level owing to the sigma-pi interaction has been demonstrated by the use of electrochemical and organochemical redox reactions. The stable cation radical and dication have successfully been generated from this anthracene derivative.