EXPLOITATION OF CORE MOLECULES FOR SPIN-DEPENDENT SINGLE MOLECULAR DEVICES

自旋相关单分子器件核心分子的开发

• 批准号: 17550128
• 负责人: ITO Akihiro
• 金额: $ 1.98万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550128/
• 关键词: MOLECULAR ELECTRONICS; AROMATIC AMINE; NITROXIDE RADICAL; MIXED VALENCE STATE; HIGH SPIN STATE

In order to investigate the influence of the substituted functional group on the IV-CT states of the organic IV compounds, we have carried out the synthesis of a nitroxide-group-substituted meta-terpheny1-4,4"-diamine 1. It is confirmed that the radical cation of an unsubstituted meta-terphenyl-4,4"-diamine 2 can be regarded as Class II IV compound. The. nitroxide radical group as a spin-bearing unit is substituted at the 5'-position of the central phenyl ring of meta-terphenyl backbone in order to retain the symmetrical arrangement of the two redox sites. Moreover, two triarylamine redox sites and the nitroxide radical group are connected to each other via meta-linkage. It was expected that such a substitution do not-essentially affect the IV-CT between symmetrically arranged two redox-active sites as is observed in 2^+. However, in 1^+, we could not observe the characteristic IVCT absorption band at around 1500 nm observed in 2^+. Although the reason is unclear at the present stage, there exist two possible explanations : (i) the change of the electron transfer path from the IV-CT between the two triarylamine sites into the IVCT between the nitroxide radical group and one of the two triarylamine sites, and (ii) the generated charge (or spin) is completely localized on one triphenylamine site. From the theoretical consideration, however, it was strongly suggested that the charge transfer path in 1^+ is changed from one between the two triarylamine sites to one between the triarylamine site and the nitroxide radical site. In any case, the diradical cation of 1 gives an intriguing example for tuning the ICT process by functional group substitution into the bis(triarylamine) IV-CT system.

为了研究取代官能团对有机Ⅳ类化合物Ⅳ-CT态的影响，我们合成了一种氮氧基团取代的间三联苯-4，4”-二胺1.经证实，未取代的间三联苯-4，4”-二胺2的自由基阳离子可被视为II-IV类化合物。的.作为自旋承载单元的氮氧自由基基团在间三联苯骨架的中心苯环的5 ′-位被取代，以保持两个氧化还原位点的对称排列。此外，两个三芳基胺氧化还原位点和氮氧自由基基团通过间位键彼此连接。预计这种取代不会像在2^+中观察到的那样，对对称排列的两个氧化还原活性位点之间的IV-CT产生实质性影响。然而，在1^+中，我们无法观察到在2^+中观察到的在1500 nm附近的特征IVCT吸收带。虽然原因目前尚不清楚，但存在两种可能的解释：（i）电子转移路径从两个三芳基胺位点之间的IV-CT变为氮氧自由基基团与两个三芳基胺位点之一之间的IVCT，以及（ii）产生的电荷（或自旋）完全局限于一个三苯胺位点。然而，从理论上考虑，强烈建议1^+中的电荷转移路径从两个三芳胺位点之间的路径改变为三芳胺位点和氮氧自由基位点之间的路径。在任何情况下，1的双自由基阳离子给出了一个有趣的例子，用于通过官能团取代到双（三芳基胺）IV-CT系统中来调整ICT过程。

项目成果

The Poly(Radiacal Cation) of a Star-Shaped Oligoarylamine -Detection of Excited High-Spin States

星形寡芳胺的聚（自由基阳离子）-激发的高自旋态的检测

• 发表时间: 2007
• 期刊: European Journal of Organic Chemistry 2007・1
• 作者: Kayo Terada;Fumio Sanda;Toshio Masuda;Ito Akihiro
• 通讯作者: Ito Akihiro

The Poly(Radiacal Cation) of a Star-Shaped Oligoarylamine- Detection of Excited High-Spin States

星形寡芳胺的聚（自由基阳离子）-激发的高自旋态的检测

• 发表时间: 2007
• 期刊: European Journal of Organic Chemistry 2007.1
• 作者: Y.Hirao;H.Ishizaki;A.Ito;T.Kato;K.Tanaka
• 通讯作者: K.Tanaka

The Poly(Radiacal Cation) of a Star-Shaped Oligoarylamine - Detection of Excited High-Spin States

星形低聚芳胺的聚（自由基阳离子）-激发的高自旋态的检测

• 发表时间: 2007
• 期刊: European Journal of Organic Chemistry 2007・1
• 作者: Y.Hirao;H.Ishizaki;A.Ito;T.Kato;K.Tanaka;Akihiro Ito
• 通讯作者: Akihiro Ito

Triradical Cation of p-Phenylenediamine Having Two Nitroxide Radical Groups : Spin Alignment Mediated by Delocalized Spin

具有两个硝基氧自由基基团的对苯二胺的三自由基阳离子：离域自旋介导的自旋排列

• 发表时间: 2006
• 期刊: Journal of the American Chemical Society 128・9
• 作者: Y.Hirao;H.Ishizaki;A.Ito;T.Kato;K.Tanaka;Akihiro Ito;Ito Akihiro
• 通讯作者: Ito Akihiro

High-Spin Radical Cations of a Dendritic Oligoarylamine

树枝状低聚芳胺的高自旋自由基阳离子

• 发表时间: 2006
• 期刊: Journal of Physical Chemistry A 110・14
• 作者: Y.Hirao;H.Ishizaki;A.Ito;T.Kato;K.Tanaka;Akihiro Ito;Ito Akihiro;Ito Akihiro
• 通讯作者: Ito Akihiro