Synthesis, Structure, Function, and Application of New Highly Strained Compounds

我们在1984-1986年间进行了题为项目的研究。1.合成了三个环状聚钙烯，并根据~lt；^1H&gt；和~lt；~(13)C&gt；-核磁共振波谱数据，结合分子轨道和图论计算，研究了它们的基态电子结构。在所有的情况下都发生了芳香族稳定化，但随着钙烯单元数量的增加，芳香族稳定化的程度趋于降低。钙铝石烯单元极化产生的环丙烯和环戊二烯离子的大-lt；pi&gt；共轭对整个体系的稳定起着重要的作用。合成了具有较强给电子能力的1，3-二硫醚[4]-和[6]-弧烯。特别是与四氟取代物[4]形成了具有较高电导率的CT络合物(&lt；10^(-2)&gt；10^(-1)&gt；S/cm)。硫杂蒽基[3]放射烯为I…基于其高度的平面性和预期的给电子能力，更多地以蓝色晶体的形式存在，有望成为合成金属的理想电子给体。合成了同时具有给体和受体基团的降冰片二烯(DA-NBD)。它们在可见光区由于电子的CT跃迁而消光，在CT波段照射后，它们定量地异构化成相应的四环(DA-Q)，量子效率很高。用这种新型光致变色体系制备了光致变色PMMA固体薄膜。值得注意的是，胶片中化学振荡的重复性非常高。合成了多环芳香族化合物及其戊烯异构体之间的光致变色反应新体系。1，2，3-三叔丁基萘、异喹啉和菲在光解条件下得到了它们的戊烯异构体。戊烯异构体动力学稳定，是典型的“P型”光致变色体系。较少

We have performed our research with the titled project for the period of 1984-1986. The following results were obtained:1. The three cyclic polycalicenes were synthesized, and their electronic structures in the ground state were investigated on the basis of <^1H> - and <^(13)C> -NMR spectral data, and also of molecular orbital and graph theoretical calculations. In all the cases aromatic stabilization occurs, although the degree tends to decrease with an increasing number of calicene unit. The large <pi> conjugation of cyclopropenium and cyclopentadienyl ions produced by polarization of each calicene unit plays an important role on the stabilization of the total <pi> system.2. 1,3-Dithiole[4]- and [6]-radialenes were synthesized, which have strong electron-donating ability. In particular, with TCNQ and its tetrafluoro derivative the [4]radialenes formed CT complexes, whose electrical conductivities are considerably high ( <10^(-2)> - <10^(-1)> S/cm). The thioxanthenyl[3]radialene was i … More solated as blue crystals, which can be expected as a desirable electron donor for synthetic metals, on the basis of its high planarity and expected electron-donating ability.Norbornadienes possessing both donor and acceptor groups (DA-NBD) were synthesized. They revealed an extinction at visible region due to CT transition of electrons, and upon irradiation at the CT band they isomerized to the corresponding quadricyclanes (DA-Q) quantitatively with high quantum efficiency. Photochromic solid PMMA films doped with this new type of photochromic systems were prepared. Noteworthy is the remarkably high repetitionality of the chemical oscillations in the film.4. New photochromic systems based on photochemical interconversion between polycyclic aromatic compounds and their valene isomers were prepared. 1,2,3-tri-t-butyl-naphthalene isoquinoline and anthracene gave their valene isomers photolytically. The valene isomers were kinetically stable, and thus, these systems were found to be typical "P Type" photochromism. Less