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Development of molecular devices and room-temperature supercondoctors by using discotic liquid crystals of organic transition metal complexes

利用有机过渡金属配合物盘状液晶开发分子器件和室温超导体

基本信息

批准号：
02044060
负责人：
YAMAMOTO Iwao
金额：
$ 3.39万
依托单位：
shinshu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

Octa (dodecyl) tetrapylazitioporphylazine (C_<12>)_8P_zH_2, the corresponding metal (II) complexes (C_<12>)_8P_zM, M : Cu, Ni, Co, octa (2-etliylliexyl) tetrapylazinoporphyrazine (2-EtC_6)_8P_zH_2 and the corresponding copper (II) complex (2-EtC_6)_8PzCu have been synthesized and their liquid crystalline statescharacterized. These properties have been compared to those of the corresponding plillialocyanines. The metal free (C_<12>)_8P_zH_2 derivative forms a hexagonal disordered columnar mesophases (D_<hd>)like (C_<12>)_8PcH_2, whereas (C_<12>)_8P_zM (M : Cu, Ni, Co) lead to centered rectangular disordered columnar mesophases (D_<rd>). The branched chain substituted metal free derivative (2-EtC_6)_8P_zH_2 leads to a tetragonal mesophase as (2-EtC_6O)_8PcCu forms an oblique mesophase, whereas (2-EtC_6O)_8PzCu leads to an unidentified liquid crystal. The tetrapyrazinoporphyrazine compounds are the first pi-acceptor columnar mesogens ; the half-wave reduction potentials are -0.41V for (C_<12>)_8P_zH_2 and -0.55V for (C_<12>)_8 P_zM (M : Cu, Ni). In comparison, plitalocyanine derivatives are reduced at -0.94V for (2-EtC_6O)_8PcH_2 and -1.05V for (2-EtC_6O)_8PcZn.Octakis (alkyloxyphenyl) -phtarocyanine derivatives ( (C_nOph)_8PcH_2=8, 10, 12 and 18), their corresponding copper (II) complexes ( (C_nOph)_8PcH_2n=10, 12 and 18) and oktakis (2-ethylhexyl) PcH_2 have been synthesized and their mesomorphic properties characterized. (C_nOph)_8PcH_2, (n=12 and 18) exhibit hexagonal disordered columnar mesophases where (C_nOph)_8PcCu(n=12 and 18) yields a rectangular disordered columnar liquid crystal. Analkylphenyloxymethyl derivative, (C_<12>phOCH_2, was synthesized to determine the influence of the connecting link between the side chains aild the phtalocyanine macrocycle on the mesomorphic properties.

八（十二烷基）四吡唑并卟啉（C_<12>）_8P_zH_2，相应的金属（II）配合物（C_<12>）_8P_zM，M：合成了Cu、Ni、Co、八（2-乙基己基）四吡嗪并卟啉（2-EtC_6）_8P_zH_2及相应的铜（Ⅱ）配合物（2-EtC_6）_8P_zCu，并对其液晶态进行了表征。这些属性已被比较到相应的plillialocyanines。无金属的（C_<12>）_8P_zH_2衍生物形成类似于（C_）_8PcH_2的六方无序柱状中间相（D_<hd>）<12>，而（C_<12>）_8P_zM（M：Cu，Ni，Co）则形成中心矩形无序柱状中间相（D_<rd>）。（2-EtC_6）_8P_zH_2形成四元液晶相，（2-EtC_6O）_8P_zCu形成斜向液晶相，而（2-EtC_6O）_8P_zCu形成未鉴定的液晶相。四吡嗪并吡嗪化合物是第一批π受体柱状介晶，（C_<12>）_8P_zH_2和（C_<12>）_8P_zM（M：Cu，Ni）的半波还原电位分别为-0.41V和-0.55V。相比之下，普利匹林衍生物在-0.94V下还原，（2-EtC_6O）_8PcH_2和-1.05V（2-EtC_6O）_8PcZn.Octakis（烷氧基苯基）-酞菁衍生物（（C_nOph）_8PcH_2=8，10，12和18），它们相应的铜（II）配合物合成了（C_nOph）_8PcH_2n=10，12，18）和八（2-乙基己基）PcH_2，并对其介晶性质进行了表征。（C_nOph）_8PcH_2（n=12和18）为六方无序柱状液晶，（C_nOph）_8PcCu（n=12和18）为矩形无序柱状液晶。合成了一种烷基苯氧甲基衍生物（C_<12>phOCH_2），研究了侧链间的连接键和邻苯二甲酰大环对介晶性质的影响。