Synthesis, Structure, and Properties of New Conjugated pi-Electronic Systems

我们已经研究了[3]超双亲相1及其低同源物多桥[3_n]环双亲相（n=3-5）的跨环pi-pi相互作用、构象行为和光化学性质。尽管付出了很大的努力，六棱柱烷3到目前为止还没有合成出来。我们用多桥[3_n]环烷辐照研究了六棱柱体骨架的形成。在水饱和的CH_2Cl_2溶液中，用低压汞灯照射[3_3（1,3,5）环烷2，得到了一种具有双戊二烯骨架的笼状化合物。同样地，[3_3]（1,2,4,5）环烷4产生了一种新的笼型二醇，其骨架与金刚石烷相似。在这两种情况下，辐照可能首先产生高度应变的六棱柱烷衍生物，但它们立即质子化生成阳离子，这些阳离子重排为应变较小的阳离子。最稳定的阳离子被水的攻击截获，生成羟基化合物。多桥[3_n]环烷与TCNQ形成晶体电荷转移配合物。研究了供体和受体的堆叠方式对电导率的相对依赖性。1: TCNQ（1:1）复合物的电导率较低，这是由于供体和受体交替堆叠所致。合成了多桥[3_n]环烷（n=2-4）的单核Ru^<2+>和0s^<2+>配合物，并研究了它们的电化学性质。然后合成并表征了4的二核Ru（II）配合物，通过电化学还原形成其混合价离子Ru(II)- Ru(O)。电导率的测量正在进行中。我们还开发了新的环烷合成反应，如光脱碳反应和CO_2插入反应。

We have been studied transannular pi-pi interaction, conformational behavior, and photochemical properties of [3]superphane 1 and its lower homologs, multibridged [3_n]cyclophanes (n=3-5). Despite much effort, hexaprismane 3 has eluded synthesis so far. We studied the formation of the hexa-prismane skeleton by irradiating multibridged [3_n]cyclophanes. irradiation of [3_3 (1,3,5)cyclophane 2 with a low pressure Hg lamp in a water-saturated CH_2Cl_2 solution gave a new cage compound with bishomopentaprismane skeleton. Similarly [3_3](1,2,4,5)cyclophane 4 afforded a nove1 cage diol, whose skeleton is similar to that of diamantane. In both cases, irradiation may first afford highly strained hexaprismane derivatives, but they are immediately protonated to give cations, which are rearranged to the less strained cations. The most stable cations are intercepted by an attack of water to give hydroxyl compounds.The multibridged [3_n]cyclophanes formed crystalline charge transfer complexes with TCNQ.The relative dependence of the electric conductivity on the stacking mode of the donar and acceptor was studied. The conductivity of the 1 : TCNQ (1 : 1) complex was low and this was ascribed to the alternate stacking of the donar and acceptor. The mono-nuclear Ru^<2+> and 0s^<2+> complexes of multibridged [3_n]cyclophanes (n=2-4) were synthesized and their electrocchemical properties were studied. Then di- nuclear Ru(II) complexes of 4 were synthesized and characterized, and their mixed-valance ion Ru(II)- Ru(O) was formed by the electrochemical reduction. Measurement of the conductivity is in progress.We also developed novel synthetic reactions of cyclophanes such as photodecarbonylation and CO_2 insertion reactions.