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.

该项目的目的之一是合成纳米级平面π电子化合物并研究其性质，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，还研究了通过高反应性三维共轭多炔的生成和环化在溶液或气相中合成富勒烯，及其在生成高级富勒烯和杂富勒烯中的应用。关于扩展石墨的合成- 类似 pi 系统，制备外部大环化合物及其聚集行为；解决方案进行了研究。结果表明，这些分子在非极性溶剂中由于π-π堆积相互作用而缔合形成二聚体。相反，它们在极性溶剂中形成具有纳米管状结构的较高聚集体，这主要是由于疏溶剂相互作用。另一方面，开发了核心六乙炔基苯衍生物的有效合成方法，用于合成石墨烯基序分子的前体。此外，还研究了引入碳-碳三键、生成高活性中间体以及将其作为过渡金属配合物拦截的新方法。在多环多炔合成富勒烯方面，我们成功检测到了C_<60>离子用于聚炔前驱体的激光解吸质谱分析。该方法成功检测了二氮杂富勒烯C_<58>N_2和低富勒烯C_<36>。然而，通过前体的热解和炉激光分解来制备宏观量的C_ 60 的尝试没有成功。关于多炔环化，研究了二芳基二烯炔的热环化以形成多环芳族化合物。

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。