Creation of New pi-Electron Systems with Novel Properties and Functions

创建具有新特性和功能的新型 pi 电子系统

• 批准号: 04453027
• 负责人: IYODA Masahiko
• 金额: $ 4.54万
• 依托单位: Tokyo Metropolitan University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453027/
• 关键词: conductivity; Ferromagnetic interaction; donor; tetrathiafulvalene; ferrocene; palladium catalyzed reaction; cross-coupling; radical salt; 半導体; [3]ラジアレン; アフセプター; ジアニオン; CT錯体

In order to create the compounds which have both conductivity and ferromagnetic properties, we designed the donor systems bearing TTF- or ferrocene-unit at the 1,3-or 1,3,5-positions of aromatic rings. The donor molecules with TTF-units have been synthesized using the palladium-catalyzed cross-coupling reaction of tetrathiafulvalenyltin with halogenated benzene derivatives. The dication diradicals and trication triradicals prepared from the TTF-donors show conductivity like a semi-conductor. However, these radical salts indicate almost no ferromagnetic interaction between radical centers. The donor molecules with ferrocene-units have been synthesized by the palladium-catalyzed cross-coupling reaction of ferrocenylzinc reagent with halogenated benzene derivatives. This reaction easily produces the products in a one-pot procedure. The dication diradical or trication triradical salts of the ferrocenedonor show some interaction of ferrocenyl irons. However, the conductivity measurements of this system indicate that the radical salts are a insulator.

为了创建具有电导率和铁磁特性的化合物，我们在1,3或1,3,5位置的芳族环上设计了带有TTF-或二兴单元的供体系统。使用Tetrathiafulvalenyltin与卤代苯衍生物的钯催化的交叉偶联反应合成了具有TTF-UNIT的供体分子。用TTF-Donors制备的DIRATIC DIRADICAL和TRITACTIC三位一体显示出像半导体一样的电导率。但是，这些自由基盐几乎没有激进中心之间的铁磁相互作用。与甲基苯基试剂与卤代苯基衍生物的钯催化的交叉偶联反应合成了具有二代渐新基的供体分子。该反应很容易在一锅过程中产生产品。二甲苯二烯酸的脏盐或三个自由基盐表现出某种相互作用的亚铁丙烯基熨斗。但是，该系统的电导率测量表明自由基是绝缘子。

项目成果

Masahiko Iyoda: "Synthesis of (1,5-Diazabicyclo 4.3.0 nonan-2-ylidene-pentacarbonylchromium and -tungsten Using Reaction of Carbene Complexes with 6-Membered Hydrazine" Chem.Lett.777-778 (1994)

Masahiko Iyoda：“利用卡宾配合物与 6 元肼的反应合成 (1,5-二氮杂双环 4.3.0 壬基-2-亚基-五羰基铬和钨”Chem.Lett.777-778 (1994)

Hiroyuki Higuchi: "Synthesis of 1-(2,2-Dicuamoyimyl)-,1-(2,4,4-Tricyano-1,3-butadienyl)-,1,6-Bis(2,2-dicyanovinyl)-1,3,5-cycloheptatriene and Their Vinylogs" Bull.Chem.Soc.Jpn.66. 275-281 (1993)

Hiroyuki Higuchi：“1-(2,2-二氰基乙烯基)-,1-(2,4,4-三氰基-1,3-丁二烯基)-,1,6-双(2,2-二氰基乙烯基)-1的合成

Masato Yoshida: "Convenient Preparation and Michael Reactions of 4-Fluoroalkylated But-2-en-4-olides" J.Chem.Soc.,Perkin Trans.1. 501-504 (1993)

Masato Yoshida：“4-氟烷基化 But-2-en-4-oleides 的便捷制备和迈克尔反应”J.Chem.Soc.，Perkin Trans.1。

Masahiko Iyoda: "Synthesis of the Tris(9-fluorenylidene)cyclopropane Dianion and Related Dianions:〔3〕Radialenes with Novel Electronic Properties" Angew.Chem.,Int.Ed.Engl.32. 89-90 (1993)

Masahiko Iyoda：“三(9-亚芴基)环丙烷二价阴离子和相关二价阴离子的合成：[3]具有新颖电子特性的放射烯”Angew.Chem.，Int.Ed.Engl.32 (1993)。

Hideki Saitoh: "Crystal Structures of the Room-Temperature Phase of 4,4''-Difluoro-p-terphenyl and 4,4'''-Difluoro-p-quaterphenyl" Bull.Chem.Soc.Jpn.66. 2847-2853 (1993)

Hideki Saitoh：“4,4-二氟对三联苯和 4,4-二氟对四联苯的室温相的晶体结构”Bull.Chem.Soc.Jpn.66。