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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-59430017/
• 关键词: Cyclic polycalicene; Polarization; Radialene; Electron donor; Norbornadiene; Photochromism; Photo-isomerization; フォトクロミズム; 高歪化合物; シクロプロペニウムイオン; ビシクロブタン; 複素環合成; 原子価異性; 可逆的情報記録材料; 導電材料

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

我们在1984年至1986年期间对该项目进行了研究。获得了以下结果：1.合成了三种环状聚杯烯，并利用核磁共振氢谱和碳谱数据，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，芳香稳定发生，虽然程度往往随着杯芳烃单元的数量增加而降低。每个<pi>杯烯单元极化产生的环丙烯鎓离子和正离子的大共轭对整个体系的稳定起着重要的作用<pi>.合成了具有强给电子能力的1，3-二硫杂环戊烯[4]-和[6]-。特别地，[4] radialene与TCNQ及其四氟衍生物形成CT络合物，其电导率相当高（&lt;10^（-2）&gt; - &lt;10^（-1）&gt; S/cm）。硫杂蒽基[3]radialene， ...更多信息 由于其高的平面性和预期的给电子能力，可以作为合成金属的理想给电子体，合成了同时具有给体和受体基团的降冰片二烯（DA-NBD）。它们揭示了由于电子的CT跃迁而在可见光区发生消光，并且在CT波段照射后，它们以高量子效率定量地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体系的光致变色固体PMMA薄膜。值得注意的是，在电影中的化学振荡的显着高重复性。利用多环芳香族化合物与其价烯异构体之间的光化学相互转化反应，制备了新型光致变色体系。1，2，3-三叔丁基萘异喹啉和蒽光解生成其价烯异构体。这些化合物具有动力学稳定性，属于典型的P型光致变色体系。少

项目成果

Hngew.Chem.97. (1985)

Hngew.Chem.97。

Shigeo Yoneda: "A Novel Aromatic Hydrocarbon with 16 <pi> -Electron Periphery: "Cyclic Bicalicene"" Angew. Chem.23. 63-64 (1984)

Shigeo Yoneda：“一种具有 16 <pi> -电子外围的新型芳香烃：“环状 Bicalicene””Angew。

Toyonari Sugimoto: "Electronic Structure of Cyclic Bicalicenes" J. Am. Chem. Soc.108. 7032-7038 (1986)

Toyonari Sugimoto：“环状 Bicalicenes 的电子结构”J. Am。

Zen-ichi Yoshida: J.Photochem.29. 27-40 (1985)

吉田善一：J.Photochem.29。

Tsunetoshi Kobayashi: Chem.Phys.Lett.125. 586-588 (1986)

小林常俊：Chem.Phys.Lett.125。