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

新型高应变化合物的合成、结构、功能及应用

基本信息

批准号：
59430017
负责人：
YOSHIDA Zen-ichi
金额：
$ 19.07万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1984
资助国家：
日本
起止时间：
1984 至 1986
项目状态：
已结题

项目摘要

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

我们已经在1984 - 1986年的标题项目中进行了研究。获得以下结果：1。合成了三个环状多晶元，并根据<^1H> - 和<^（13）C> -NMR光谱数据以及分子轨道和图理论计算研究了其基态的电子结构。在所有情况下，都会发生芳香稳定，尽管该程度随着钙髓单位数量的增加而趋于降低。每个钙烯单元极化产生的环丙基和环戊二烯基离子的大型共轭在稳定总<pipi> System.2中起着重要作用。2。合成了1,3-二硫代[4] - 和[6] - 放射烯，具有强大的电子能力。特别是，使用TCNQ及其四氟衍生物[4] radialenes形成CT复合物，其电导率很高（<10^（ - 2）> - <10^（ - 1）> s/cm）。硫氰基[3] radialene是我…更固化为蓝色晶体，可以根据其高平面性和预期的电子持持续能力来期待合成金属的理想电子供体。合成了诺伯达烯的潜在捐助者和受体组（DA-NBD）。他们揭示了由于电气的CT过渡而在可见区域的延伸，并且在CT频段进行照射后，它们会用高量子效率定量地定量地升至相应的四四形群集（DA-Q）。准备了与这种新型的光致变色系统掺杂的光致变色固体PMMA膜。值得注意的是电影中化学振荡的重复性非常高。4。制备了基于多环芳族化合物及其瓦莱纳异构体之间的光化学互转换的新的光致变色系统。 1,2,3-tri-t叔丁基异喹啉和蒽的光水解给了瓦莱纳异构体。瓦莱纳异构体在动力学上是稳定的，因此，这些系统被发现是典型的“ P型”光色素。较少的