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

我们于1984-1986年进行了该课题的研究，取得了以下成果： 1．合成了三种环状聚碳烯，并根据<^1H>研究了它们的基态电子结构。 -和<^(13)C>-NMR光谱数据，以及分子轨道和图理论计算，在所有情况下都会发生芳香族稳定化，尽管程度随着芳香族数量的增加而降低。每个二烯单元极化产生的环丙烯和环戊二烯基离子的大<pi>共轭对整个<pi>体系的稳定起着重要作用。2．合成了具有强给电子能力的]-放射烯，特别是与TCNQ及其四氟衍生物形成的[4]放射烯配合物，其电学性质良好。电导率相当高（<10^(-2)> - <10^(-1)> S/cm）。噻吨基[3]辐射烯呈蓝色晶体，可以预期是理想的电子。合成金属的供体，基于其高平面性和预期的给电子能力。合成了同时具有供体和受体基团的降冰片二烯（DA-NBD），它们在可见光区域显示出消光。电子的 CT 跃迁，在 CT 波段照射下，它们以高量子效率定量异构化为相应的四环烷 (DA-Q)，制备了掺杂这种新型光致变色系统的光致变色固体 PMMA 薄膜，值得注意的是其重复性非常高。 4．制备了基于多环芳香族化合物及其戊烯异构体光化学互变的新型光致变色体系。 1,2,3-三叔丁基萘异喹啉和蒽通过光解得到其瓦烯异构体，瓦烯异构体是动力学稳定的，因此，发现这些体系具有典型的“P型”光致变色性。