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能研究

• 批准号: 09640700
• 负责人: OGURA Fumio
• 金额: $ 1.98万
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640700/
• 关键词: Organic Electric Conductors; Charge-Transfer Complexes; Organic electron Donors; Organic Electron Acceptors; Pleiadiene Derivatives; Tellurophene-TCNO; Phenanthrene-TCNQ; Chrysene-TCNQ; 新規有機電子供与体; 新規有機電子受容体; ヘテロ-TCNQ; 16族ヘテロ原子化合物; 芳香族π-電子系化合物

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 7pi electron rings fused to a naplithalenene 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 and are first dichiorinated its peri-positins then transformed its 5-membered ring to a cyclic anhydride via bromination with NBS and the following oxidation. The diol obtained by LAH reduction of the anhydride was transformed to 1, 8-Bis(dibromomethyl)4, 5-dichioronaphthalene. The dibromide was reacted with cis-4, 5-bis(boryl)octene, prepared from bis[pinacolato]diboron and 4-octyne, to yield a pleiadene. Efforts to obtain 1 (R=n-Pr) in progress. Tellurophene-TCNQs (2) are only ones left unknown amoung Hetero-TCNQs. Synthesis of … More 2 is started from tellurophene, which is prepared by 1,4-bis(TMS)-1, 3-butadiyne and Na_2Te and then converted to 2, 5-dicarboxylic acid via 6 steps. Transformation of carboxyl group to dicyanomethylene group to obtain 2 (xl, R=H) is now actively sudying. Crysene-TCNQ (3) has a unique extended conjugated pi-system and expected to be very stable and have very low coulombic repulsion in their oxidation states. Their synthesis are planned to couple a 2-bromo-6-methoxynaphthalene and 2-bromo-5-methoxybenzaldehyde by Suzuki-Miyaura method to yield a key intermediate to lead 2, 8-dimethoxyclirysene. The coupling reaction is now scrutinized. Phenanthrene-TCNQ (4) is unique and assumed to be a strong acceptor, because it has a oquinoid partial structure. Its synthesis is planned to execute via a biphenyl derivative, which is obtained from 2-bromo-5-methoxytoluene and N,N-diethy1-4-methoxybenzamide by a combination of Suzuki-Miyaura and Snieckus coupling methods. The biphenyl derivative is subjected to metalatation, intramnoleculari condensation followed dehydroxylic elimination to afford a key phenanthrene derivative, 3, 6-dimethoxyphenanthrene. Now we are actively investigating coupling reaction conditions and procedures to obtain the biphenyl derivatives. Although we do not yet have the target molecules in our hands, we are closely approaching our targets and very sure to be able to get them in near future. Less

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带有两个7 π电子环，在其两个近位与萘稠合，并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，先将其邻位二氯化，再将其五元环与NBS溴化，最后氧化成环酐，合成了1。将酸酐经LAH还原得到的二醇转化为1，8-双（二溴甲基）4，5-二氯萘。该二溴化物与由双[频哪醇合]二硼和4-辛炔制备的顺式-4，5-双（硼基）辛烯反应，得到七曜烯。正在努力获得1（R=n-Pr）。Tellurophene-TCNQs（2）是目前唯一一个尚不清楚的杂环TCNQs。合成 ...更多信息 2是以碲吩为原料，经1，4-二（TMS）-1，3-丁二炔和碲酸钠反应制得碲吩，再经6步反应制得2，5-二羧酸。将羧基转化为二氰基亚甲基得到2（xl，R=H）的反应正在积极进行中。Crysene-TCNQ（3）具有独特的扩展共轭π-体系，预期非常稳定，并且在其氧化态下具有非常低的库仑排斥。它们的合成计划是通过Suzuki-Miyaura法将2-溴-6-甲氧基萘和2-溴-5-甲氧基苯甲醛偶联，得到2，8-二甲氧基甲基萘的关键中间体。现在仔细检查偶联反应。菲-TCNQ（4）是一个独特的强受体，因为它具有醌型部分结构。其合成计划通过联苯衍生物进行，联苯衍生物通过Suzuki-Miyaura和Snieckus偶联方法的组合由2-溴-5-甲氧基甲苯和N，N-二乙基-4-甲氧基苯甲酰胺获得。该联苯衍生物经金属间化合物、分子内缩合、脱羟基消去得到关键的菲衍生物3，6-二甲氧基菲。目前，我们正在积极研究偶联反应的条件和方法，以获得联苯衍生物。虽然我们手中还没有目标分子，但我们正在接近我们的目标，并且非常肯定能够在不久的将来获得它们。少

项目成果

Takimiya Kazuo: "Syntheses, Unique Strained Molecular Structures, and Unusual Transannular Electronic Interactions of a Series of Crisscross-Overlapped Tetrathiafulvalenophanes" The Journal of Organic Chemistry. 62(16). 5567-5574 (1997)

Takimiya Kazuo：“一系列纵横交错的四硫富瓦烯芬的合成、独特的应变分子结构和不寻常的跨环电子相互作用”有机化学杂志。

Arai Emiko: "Novel Stable Metallic Salts on a Donor Molecule Containing peri-Ditellurium Bridges, TMTTeN" Inorganic Chemistry. 37(12). 2850-2851 (1998)

Arai Emiko：“含有周二碲桥的供体分子上的新型稳定金属盐，TMTTeN”无机化学。

Aso Yoshio(安蘇 芳雄): "3,3-Thienylene-ethynylene oligomers" Phosphorus,Sulfur,and Silicon and the Related Elements. 120 & 121. 417-418 (1997)

Aso Yoshio：“3,3-噻吩基-乙炔低聚物”磷、硫和硅及相关元素。120 和 121。417-418 (1997)。

Takimiya Kazuo: "Syntheses and Properties of 11, 11, 12, 12-Tetracyano-2, 6-anthraquinodimethane(TANT) and Its 9, 10-Dichloro Derivative as Novel Extensive Electron Acceptors" Bull.Chem.Soc.Jpn.71(6). 1431-1435 (1998)

Takimiya Kazuo：“作为新型广泛电子受体的 11, 11, 12, 12-四氰基-2, 6-蒽醌二甲烷 (TANT) 及其 9, 10-二氯衍生物的合成和性能” Bull.Chem.Soc.Jpn.71(

Emiko Arai, et al.: "Novel Stable Matallic Salts on a Donor Molecule Containing peri-Ditellurium Bridges, TMTTeN." Inorganic Chemistry. 37 (12). 2850-2851 (1998)

Emiko Arai 等人：“含有周二碲桥的供体分子上的新型稳定金属盐，TMTTeN”。