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

新型有机电子给体、受体及其电荷转移络合物的合成及其性质研究

• 批准号: 11640592
• 负责人: OGURA Fumio
• 金额: $ 2.3万
• 依托单位: KINKI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640592/
• 关键词: Organic Electric Conductors; Charge-Transfer Complexes; Organic electron Donors; Organic Electron Acceptors; Pleiadiene Derivatives; Tellurophene-TCNQ; Phenanthrene-TCNQ; Chrysene-TCNQ

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

该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），它们有望作为形成具有高电导率的电荷转移复合物的有效成分。该分子 1 带有两个在其两个周边位置与萘稠合的 7π 电子环，预计在两阶段氧化还原过程中充当良好的电子供体。 1的合成是从苊开始的。通过5个反应步骤将其转化为1,8-双(二溴甲基)-4,5-二氯萘。该二溴化物与由双[频那醇]二硼和4-辛炔制备的顺-4,5-双(硼基)辛烯反应，得到芴烯衍生物。然而，收率非常低，并且没有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7元环。我们通过后一种方法合成了苊二烯 (5, R=H) 和苊二烯 (6, R=H)，并通过 CV 测量发现 5( … More R=H) 显示出与 TTF 相当的 1^<at> 氧化峰。通过昴二烯获得1(R=H)的努力正在进行中。 Tellurophene-TCNQ（2，n=1，R=H）是Hetero-TCNQ中唯一未知的，2的合成是从Tellurophene开始的。经过3个反应步骤将其转化为2,5-双(羟甲基)衍生物。目前正在积极研究将羟甲基转化为二氰亚甲基以获得2(n＝1，R＝H)。 Chrysene-TCNQ 和 -quinone (3) 具有独特的扩展共轭 π 系统，预计非常稳定，并且在氧化态下具有非常低的库仑排斥力。其关键中间体2,8-二甲氧基的合成计划已取得进展。关键化合物是在相当短的反应步骤中获得的，现在正在仔细检查其向 3 的转化。菲-TCNQ 和-醌 (4) 是独特的，被认为是强受体，因为它们具有阿醌部分结构。其通过3,6-二溴-或3,6-二甲氧基-菲的合成计划已成功执行。两种关键中间体均由相应的联苯以良好的收率获得。通过二氰甲基阴离子取代原关键化合物中的溴并进行氧化反应，得到了一种对常见有机溶剂溶解度很低的绿色固体化合物4(R=C(CN)_2)，目前正在积极研究其结构和性质。JA01K Less

项目成果

Shinobu Inoue, et al.: "Syntheses, Spectroscopic Properties, and Polymerization of 2,2'-Bitellurophene, 2,2' : 5'2"-Tertellurophene, and Related Hybrid Terchalcogenophenes."Heterocycles. 52 (No.1). 159-170 (2000)

Shinobu Inoue 等人：“2,2-二特碲吩、2,2: 52"-特碲吩和相关杂化三卤代酚的合成、光谱性质和聚合。”Heterocycles. 52（第 1 期）。

Fumio Ogura et al.: "Preparation of Organic Conductors. Organoselenium Chemistry. A Practical Approach. (ed. by T.G.Back), Chapter 14"Oxford University Press. 257-289 (1999)

Fumio Ogura 等人：“有机导体的制备。有机硒化学。实用方法。（由 T.G.Back 编辑），第 14 章”牛津大学出版社。

Takimiya Kazuo(瀧宮和男): "Synthesis, Structures, and Properties of a Series of Double-Bridged Tetrathiafulvaleno-phanes as Noyel Electron Donors for Conductive Radical Cation Salts"Chemistry of Materials. 12. 2196-2204 (2000)

Kazuo Takimiya：“作为导电自由基阳离子盐的 Noyel 电子供体的一系列双桥四硫富瓦烯芬的合成、结构和性能”《材料化学》12。2196-2204 (2000)。

Ojima Emiko(小島恵美子): "New Stable Metallic Salt Based on a Donor Molecule Containing peri-Ditellurium Bridges, TMTTeN(SCN)_<0.88>"Chemistry Letters. 8. 845-846 (1999)

Emiko Ojima：“基于含二碲桥的供体分子的新型稳定金属盐，TMTTeN(SCN)_<0.88>”《化学快报》8. 845-846 (1999)

Ogura Fumio(小倉文夫): ""Preparation of Organic Conductors" in "Organoselenium Chemistry" ed by T.G.Back, Chapter 14,"Oxford University Press. 21 (1999)

Ogura Fumio：“T.G.Back 编辑的《有机硒化学》中的“有机导体的制备”，第 14 章，”牛津大学出版社 21 (1999)。