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

我们研究了[3]超环1及其低同系物多桥[3_n]环番(n=3-5)的跨环pi-pi相互作用、构象行为和光化学性质。尽管付出了很多努力，但到目前为止，六氢吡喃3还没有被合成出来。我们研究了多桥[3_n]环番辐照形成六柱撑骨架的过程。在水饱和的CH2Cl2溶液中，用低压汞灯照射[3_3(1，3，5)环番2]，得到一种新的具有双茂金属骨架的笼状化合物。类似地，[3_3](1，2，4，5)环番4得到了一种新的笼状二醇，其骨架类似于金刚烷。在这两种情况下，辐射可能首先得到高应变的六氢呋喃衍生物，但它们立即被质子化成阳离子，阳离子被重新排列成应变较小的阳离子。最稳定的阳离子被水截留生成羟基化合物。多桥[3_n]环番与TCNQ形成晶态电荷转移络合物。研究了电导率与多纳和受体的堆积方式的相对关系。1：TCNQ(1：1)络合物的电导率较低，这归因于多纳和受体的交替堆积。合成了多桥[3_n]环番(n=2-4)的单核Ru^&lt；2+&gt；和0^&lt；2+&gt；配合物，并研究了它们的电化学性质。然后合成并表征了4个双核Ru(II)配合物，并通过电化学还原形成了Ru(II)-Ru(O)的混价离子。电导率的测量也在进行中。我们还开发了新的环番合成反应，如光脱羰反应和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.