Development of Stable Neutral Radicals Having an Unconventional Spin-Delocalized Nature

具有非常规自旋离域性质的稳定中性自由基的发展

• 批准号: 15087202
• 负责人: MORITA Yasushi
• 金额: $ 18.43万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15087202/
• 关键词: neutral radical; open-shell molecule; odd-alternant hydrocarbon; phenalenyl; molecular magnetism; spin-delocalized nature; topological symmetry; π-dimer; スピン分極; スピン分解; 中世ラジカル; ヘテロラジカル; 芳香族性; トポロジー; 結晶構造

Organic open-shell molecules, widely recognized as short-lived reactive intermediates, have recently drawn attention as building blocks for new molecule-based functional materials, since various stabilization techniques have been developed. In order to strengthen the basis of this research field, it is crucial to establish novel design criteria and synthetic methodologies of open-shell molecular systems with structurally and electronically salient features. In this study, we have synthesized and characterized new organic open-shell systems having topologically-controlled and extremely delocalized spin-density distribution natures, demonstrating exotic electronic features originating from these electronic spin structures. (1) realization of novel thermochromism based on dynamic electron-spin behavior : We have experimentally determined chemical structure of Ti-dimer formed in a solution state at low temperature, revealing a new C-C bond with 12-center-2-electron nature. Furthermore, aromaticity of a radical aggregate was first proposed in our study. (2) realization of the switching system in terms of spin-center transfer of purely organic open-shell system : We have prepared TTF-linked 6-oxophenalenoxyl neutral radical system, and created solvent-and temperature-controlled complete spin-switching system based on intramolecular electron transfer. (3) The delocalized singlet biradical hydrocarbons were first synthesized, isolated, and characterized, showing the highest room-temperature electric conductivity as single-component hydrocarbon, and exceptionally large two-photon absorption cross sections for pure hydrocarbon with no electron-donor or-acceptor substituents.

有机开壳分子被广泛认为是短寿命的反应中间体，由于各种稳定技术的发展，最近作为新型分子功能材料的构建模块引起了人们的关注。为了加强该研究领域的基础，建立具有结构和电子显着特征的开壳分子系统的新颖设计标准和合成方法至关重要。在这项研究中，我们合成并表征了具有拓扑控制和极其离域自旋密度分布性质的新型有机开壳系统，展示了源自这些电子自旋结构的奇异电子特征。 (1)基于动态电子自旋行为的新型热致变色的实现：我们通过实验确定了低温溶液状态下形成的Ti-二聚体的化学结构，揭示了具有12-中心-2-电子性质的新C-C键。此外，我们的研究首次提出了自由基聚集体的芳香性。 (2)纯有机开壳体系自旋中心转移切换体系的实现：我们制备了TTF连接的6-氧代苯酚中性自由基体系，并创建了基于分子内电子转移的溶剂和温度控制的完整自旋切换体系。 (3)首次合成、分离和表征了离域单线态双自由基烃，其显示出单组分烃中最高的室温电导率，以及不含电子给体或受体取代基的纯烃的异常大的双光子吸收截面。

项目成果

Second hyperpolarizability of phenalenyl radical system involving acetylene π-conjugated bridge

• DOI: 10.1016/j.cplett.2006.01.022
• 发表时间: 2006-03
• 期刊: Chemical Physics Letters
• 影响因子: 2.8
• 作者: Suguru Ohta;M. Nakano;T. Kubo;K. Kamada;K. Ohta;R. Kishi;Nozomi Nakagawa;B. Champagne;E. Botek;Shin-ya Umezaki;A. Takebe;Hideaki Takahashi;S. Furukawa;Y. Morita;K. Nakasuji;K. Yamaguchi

Phenalenyl-based Highly Conductive Molecular Systems with Hydrogen-Bonded Networks : Synthesis, Physical Properties and Crystal Structures of 1,3- and 1,6-Diazaphenalenes, and Their Protonated Salts and Charge-Transfer Complexes with TCNQ

具有氢键网络的基于苯烯基的高导电分子体系：1,3-和1,6-二氮杂菲那烯及其质子化盐和与TCNQ的电荷转移配合物的合成、物理性质和晶体结构

• 发表时间: 2006
• 期刊: Bull.Chem.Soc.Jpn. (印刷中)
• 作者: Murata;T.
• 通讯作者: T.

Y.Morita: "1,3-Diazaphenalenes : A New Donor System for Hydrogen-Bonded Charge-Transfer Complexes."Synth.Met.. 135-136. 657-658 (2003)

Y.Morita：“1,3-二氮杂菲那烯：氢键电荷转移复合物的新供体系统。”Synth.Met.. 135-136。

Hydrogen-bonded networks in organic conductors: crystal structures and electronic properties of charge-transfer salts of tetracyanoquinodimethane with 4,4'-biimidazolium having multiprotonated States.

• DOI: 10.1021/jo047768c
• 发表时间: 2005-04
• 期刊: The Journal of organic chemistry
• 作者: Y. Morita;T. Murata;K. Fukui;S. Yamada;Kazunobu Sato;D. Shiomi;T. Takui;H. Kitagawa;H. Yamochi;G. Saito;K. Nakasuji

二光子吸収材料

双光子吸收材料

• 发表时间: 2012