Design and development of photo-induced organic molecular metals

光诱导有机分子金属的设计与开发

基本信息

批准号：
13450352
负责人：
TANAKA Kazuyoshi
金额：
$ 8.51万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

(1) Hybrid system composed of TTF fused with 1,3-dithiol-2-ylidene (DT TTF) and C60 (1) has been designed, and its electronic structure has been investigated. The molecular orbital calculation of the unsubstituted-1 suggests that the DT TTF and C_<60> units mainly contribute to the HOMO and LUMO, respectively. The DT TTF and C_<60> moieties have positive and negative, respectively, indicating intramolecular charge-transfer. On the other hand, HOMO-LUMO gap of 1 is significantly smaller by 3.02 and 1.07 eV compared with those of DT TTF and C_<60>, respectively.(2) Several derivatives of 1 have been synthesized. Cyclic voltammogram of 1 consists of two reversible oxidation waves corresponding to the TTF and four reduction ones due to C_<60> moiety. The oxidation potentials are higher than those of the corresponding DT TTF derivative due to electron-withdrawing effect of C_<60>. In a similar manner, the reduction potentials are more negative than those of C_<60> because of electron-donating effect of the donor moiety. They showed electrical conductivity of σ_<rt> = 10^<-8>S cm^<-1> on compressed pellets.(3) Several derivatives of oligo-fused extended-TTF, in which thiophene is inserted, have been synthesized. Cyclic voltammogram of the tris-fused derivative consists of two pairs of two-electron transfer waves and two pairs of one-electron ones, while the bis-fused analog exhibits four pairs of one-electron transfer waves. The above results indicate that the positive charges delocalize on the whole molecule. In the UV vis spectra of these oligo-fused extended-TTFs, the absorption maxima appeared around 485 nm, and no significant shift to the longer wavelength region was observed derived from increase of extended-TTF units.

（1）设计了由与1,3-二硫醇-2-甲基（DT TTF）和C60（1）融合的TTF组成的杂种系统，并研究了其电子结构。未取代1的分子轨道计算表明，DT TTF和C_ <60>单位分别主要有助于HOMO和LUMO。 DT TTF和C_ <60>部分分别具有正分子电荷转移。另一方面，与DT TTF和C_ <60>的Homo-Lumo间隙分别为3.02和1.07 EV明显小于3.02和1.07 eV。（2）已合成了1个的几个衍生物。 1的环状伏安图由两个可逆氧化波组成，与TTF相对应，而由于C_ <60>部分而引起的四个还原。氧化电位高于相应的DT TTF衍生物的氧化电位，这是由于C_ <60>的绘图效应而导致的。以类似的方式，由于供体部分的电子粉状效应，还原电位比C_ <60>的负势更为负。他们在压缩颗粒上显示了σ_<rt> = 10^<-8> s cm^<-1>的电导率。（3）插入硫芬的几种寡粉末的扩展-TTF的几种衍生物已合成，已合成。 Tris融合的衍生物的循环伏安图由两对两电子转移波和两对单电子的传动波组成，而BIS融合的类似物则表现出四对单电子传递波。以上结果表明，正电荷在整个分子上分离。在这些寡粉融合的延伸TTF的紫外线vis光谱中，吸收最大值出现在485 nm左右，并且没有观察到从扩展TTF单元的增加而导出的更长的波长区域。