SYNTHESES OF NEW ORGANIC ELECTRON DONORS, ACCEPTORS, AND THEIR CHARGE-TRANSFER COMPLEXES, AND STUDIES ON THEIR PROPERTIES

本研究项目的目标分子是新型有机电子给体（1）和受体（2，3，4），它们有望作为有效组分形成具有高电导率的电荷转移复合物。分子1在其两个邻位上带有两个与萘稠合的7 π电子环，并且预期在两阶段氧化还原过程中表现为良好的电子供体。以苊为起始原料合成1。通过5步反应将其转化为1，8-二（二溴甲基）-4，5-二氯萘。二溴化物与由双[频哪醇合]二硼和4-辛炔制备的顺式-4，5-双（硼基）辛烯反应，以产生七曜烯衍生物。然而，产率非常低，并且不能通过改变反应条件来提高。然后，我们采用分子内Friedel-Crafts型反应来构建七元环。我们用后一种方法合成了乙酰庚二烯（5，R = H）和乙酰庚二烯（6，R = H），发现5， ...更多信息 R = H）通过CV测量显示出与TTF相当的1 ^氧化峰。<at>正在努力通过七曜烯获得1（R = H）。碲吩-TCNQs（2，n = 1，R = H）是TCNQs中唯一未知的化合物。通过3步反应将其转化为2，5-双（羟甲基）衍生物。羟甲基转化为二氰亚甲基得到2（n = 1，R = H）的反应正在进行中。Chrysene-TCNQ和-醌（3）具有独特的扩展共轭π-体系，并且预期是非常稳定的，并且在其氧化态下具有非常低的库仑排斥。提出了通过关键中间体2，8-二甲氧基喹啉合成该化合物的方案。在相当短的反应步骤中获得了关键化合物，现在正在仔细检查其转化为3。菲-TCNQ和-醌（4）是独特的，并假定是一个强受体，因为它们具有醌型部分结构。通过3，6-二溴菲或3，6-二甲氧基菲的合成方案得到了成功的实施。这两个关键中间体都是从相应的联苯以良好的产率得到的。通过二氰甲基取代溴代和氧化两步反应，得到了一种对普通有机溶剂溶解度很低的绿色固体化合物4（R = C（CN）_2），我们正在对其结构和性质进行研究。JA01 K Less

The target molecules of this research projects are novel organic electron donors (1) and acceptors (2,3,4), which are expected to act as effective components to form charge-transfer complexes exhibiting high electric conductivities. The molecule, 1, carries two 7π electron rings fused to a naphthalenene at its two peri-positions and is expected to behave as a good electron donor in the two stage redox processes. Synthesis of 1 is started from acenaphthene. It was transformed to 1,8-Bis (dibromomethyl)-4,5-dichloronaphthalene by 5 reaction steps. The dibromide was reacted with cis-4,5-bis (boryl) octene, prepared from bis [pinacolato] diboron and 4-octyne, to yield a pleiadene derivative. However, the yield was very low and not improved by modification of reaction conditions. Then we have adopted the intramolecular Friedel-Crafts type reaction for construction of the 7-membered ring. We have synthesized acepleiadiene (5, R=H) and acepleiadylene (6, R=H) by the latter method and found 5( … More R=H) showed a comparable 1^<at> oxidation peak as that of TTF by CV measurement. Efforts to obtain 1(R=H) via pleiadiene are in progress. Tellurophene-TCNQs (2, n=1, R=H) are only ones left unknown among Hetero-TCNQs, Synthesis of 2 is started from tellurophene. It was converted to 2,5-bis (hydroxymethyl) derivative via 3 reaction steps. Transformation of hydroxymethyl group to dicyanomethylene group to obtain 2 (n=1, R=H) is now actively sudying. Chrysene-TCNQ and -quinone (3) have a unique extended conjugated π-system and are expected to be very stable and have very low coulombic repulsion in their oxidation states. Its synthetic plan through a key intermediate, 2,8- dimethoxychrysene, was progressed. The key compound was obtained in a fairly short steps of reaction and its conversion to 3 is now scrutinized. Phenanthrene-TCNQ and -quinone (4) are unique and assumed to be a strong acceptor, because they have a oquinoid partial structure. Its synthetic plan via 3,6-dibromo- or 3,6-dimethoxy-phenanthrene was executed with success. Both key intermediates were obtained in good yields from the corresponding biphenyls. A green solid compound, which has a very low solubility to common organic solvents, appeared to be 4 (R=C(CN)_2) was obtained by the two successive reactions, substitution of bromine of the former key compound with dicyanomethyl anion and oxidation, We are now actively studying its structure and properties.JA01K Less