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Creation of New Extended Pi-Electronic Systems Composed by Conjugated Polyynes

由共轭聚炔组成的新型扩展 Pi 电子系统的创建

基本信息

批准号：
11450346
负责人：
TOBE Yoshito
金额：
$ 9.28万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450346/
关键词：
Polyynes Fullerenes Graphite Nanotube Pi electronic systems Aromatic compounds Cyclophanes アセチレン自己会合

项目摘要

On of the purposes of this project is to synthesize planar pi-electronic compounds of nanoscale regime and to investigate their properties to elucidate novel properties of unknown carbon allotropes composed by sp and sp^2-hybridyzed carbons. In addition, synthesis of fullerenes in solution or in vapor phase by the generation and cyclizatipn of highly reactive, three-dimensional conjugate polyynes was investigated as well as its application to the generation of higher fullerenes and heterofullerenes.With regard to the synthesis of extended graphite-like pi-systems the external macrocyclic compounds were prepared and their aggregation behavior in; solution was investigated. As a result, it was revealed that these molecules associate in non-polar solvents to form dimers due to pi-pi stacking-interactions. In contrast, they formed higher aggregates having nanotube-like structure in polar solvent mainly due to solvophobic interactions. On the other hand, the efficient synthetic method for the core hexaethynylbenzene derivatives was developed which was adopted to the synthesis of precursors of graphyne motif molecules. In addition, new methods for the introduction of carbon-carbon triple bonds and generation of highly reactive intermediates and their interception as transition metal complexes were investigated.Regarding the synthesis of fullerenes from polycyclic polyynes, we succeeded in the detection of C_<60> ions in the laser-desorption mass spectrometry of polyyne precursors. This method was applied to the successful detection of diazafullerene C_<58>N_2 and lower fullerene C_<36>. However, attempts to prepare macroscopic amount of C_<60> by pyrolysis and oven-laser decomposition of the precursors were unsuccessful. In connection to the polyyne cyclization, thermal, cyclization of diaryIdienynes to form polycyclic aromatic compounds was investigated.

本项目的目的是合成纳米尺度的平面pi电子化合物，并研究它们的性质，以阐明由sp和sp^2杂化碳组成的未知碳同素异形体的新性质。此外，还研究了高活性三维共轭聚炔的生成和环合反应在溶液和气相中合成富勒烯的方法，以及在合成高富勒烯和杂富勒烯方面的应用。在合成扩展的类石墨pi-体系方面，合成了外加大环化合物，并考察了它们在溶液中的聚集行为。结果表明，由于pi-pi堆积作用，这些分子在非极性溶剂中缔合形成二聚体。相反，它们在极性溶剂中形成了具有纳米管状结构的高聚集体，这主要是由于疏水相互作用造成的。另一方面，开发了一种高效的核心六乙炔基苯衍生物的合成方法，并将其应用于接枝基元分子前体的合成。此外，还研究了碳-碳三键的引入、高活性中间体的生成及其作为过渡金属络合物截留的新方法。在多环多炔合成富勒烯方面，我们成功地检测到了聚炔前驱体激光解吸质谱学中的C&lt；60&gt；离子。该方法成功地用于二氮富勒烯C&lt；58&gt；N_2和低富勒烯C_&lt；36&gt；然而，通过前驱体的热解和烘箱-激光分解来制备宏观数量的C_(60)和C_(60)的尝试没有成功。结合聚炔的环化、热、环化反应，研究了二芳基二炔环成多环芳香化合物的反应。

项目成果

期刊论文数量（72）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Motohiro Sonoda: "Synthesis of Differentially-Substituted Hexaethynylbenzenes Based on Tandem Sonogashira and Negishi Cross-Coupling Reactions"Organic Letters. 3(15). 2419-2421 (2001)

Motohiro Sonoda：“基于串联 Sonogashira 和 Negishi 交叉偶联反应的差异取代六乙炔基苯的合成”有机快报。

DOI：
发表时间：
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影响因子：
0
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通讯作者：

Yoshito Tobe: "Synthesis and Association Behavior of Butadiyne-Bridged [4_4](2,6) Pyridinophane and [4_6](2,6) Pyridinophane Derivatives"Organic Letters. 2(21). 3265-3268 (2000)

Yoshito Tobe：“丁二炔桥联[4_4](2,6)吡啶芬烷和[4_6](2,6)吡啶芬衍生物的合成和缔合行为”有机快报。

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

Yoshito Tobe, Naoto Utsumi, Kazuya Kawabata, Atsushi Nagano, Kiyomi Adachi, Shunji Araki, Motohiro Sonoda, Keiji Hirose, and Koichiro Naemura: "m-Diethynylbenzene Macrocycles: Syntheses and Self-Association Behavior in Solution"J. Am. Chem. Soc.. 124 (in

Yoshito Tobe、Naoto Utsumi、Kazuya Kawabata、Atsushi Nagano、Kiyomi Adachi、Shunji Araki、Motohiro Sonoda、Keiji Hirose 和 Koichiro Naemura：“间二乙炔基苯大环化合物：溶液中的合成和自缔合行为”J。