纳米石墨烯表面合成中的立体选择性 [3 + 3] 环芳香化反应

IF 4.8 Q2 NANOSCIENCE & NANOTECHNOLOGY ACS Nanoscience Au Pub Date : 2023-12-22 DOI:10.1021/acsnanoscienceau.3c00062
Amogh Kinikar, Xiao-Ye Wang, Marco Di Giovannantonio, José I. Urgel, Pengcai Liu, Kristjan Eimre, Carlo A. Pignedoli*, Samuel Stolz, Max Bommert, Shantanu Mishra, Qiang Sun, Roland Widmer, Zijie Qiu, Akimitsu Narita, Klaus Müllen*, Pascal Ruffieux and Roman Fasel*, 
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引用次数: 0

摘要

表面催化反应已被用于合成具有原子预定结构的碳纳米材料。最近发现的一种金表面催化的异丙基取代茴香的[3 + 3]环芳香化反应使芳基-亚苯共聚物的表面合成成为可能,在这种反应中,表面激活异丙基取代基,通过分子间偶联形成亚苯环。然而,当两个以上的分子在一个位点发生反应时,生成的聚合物就会发生不希望发生的交联。在这里,我们展示了通过将异丙基基团连接到较大的炔核上,可以通过立体保护来防止这种交联。当异丙基取代的 8,9-二氧杂-8a-硼并[fg]四蒽在 Au(111) 上被热激活时,可以观察到环芳香化作用完全发生在两个分子之间。两个分子通过共价连接形成的环芳香化中间体被宽大的苯并四蒽核心所阻止,无法与其他分子发生反应,从而导致高选择性的一对一偶联。我们的研究结果扩展了异丙基取代基[3 + 3]环芳香化反应的多功能性,并指出立体保护是抑制表面合成中竞争反应途径的有力概念。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Sterically Selective [3 + 3] Cycloaromatization in the On-Surface Synthesis of Nanographenes

Surface-catalyzed reactions have been used to synthesize carbon nanomaterials with atomically predefined structures. The recent discovery of a gold surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituted arenes has enabled the on-surface synthesis of arylene-phenylene copolymers, where the surface activates the isopropyl substituents to form phenylene rings by intermolecular coupling. However, the resulting polymers suffered from undesired cross-linking when more than two molecules reacted at a single site. Here we show that such cross-links can be prevented through steric protection by attaching the isopropyl groups to larger arene cores. Upon thermal activation of isopropyl-substituted 8,9-dioxa-8a-borabenzo[fg]tetracene on Au(111), cycloaromatization is observed to occur exclusively between the two molecules. The cycloaromatization intermediate formed by the covalent linking of two molecules is prevented from reacting with further molecules by the wide benzotetracene core, resulting in highly selective one-to-one coupling. Our findings extend the versatility of the [3 + 3] cycloaromatization of isopropyl substituents and point toward steric protection as a powerful concept for suppressing competing reaction pathways in on-surface synthesis.

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来源期刊
ACS Nanoscience Au
ACS Nanoscience Au 材料科学、纳米科学-
CiteScore
4.20
自引率
0.00%
发文量
0
期刊介绍: ACS Nanoscience Au is an open access journal that publishes original fundamental and applied research on nanoscience and nanotechnology research at the interfaces of chemistry biology medicine materials science physics and engineering.The journal publishes short letters comprehensive articles reviews and perspectives on all aspects of nanoscience and nanotechnology:synthesis assembly characterization theory modeling and simulation of nanostructures nanomaterials and nanoscale devicesdesign fabrication and applications of organic inorganic polymer hybrid and biological nanostructuresexperimental and theoretical studies of nanoscale chemical physical and biological phenomenamethods and tools for nanoscience and nanotechnologyself- and directed-assemblyzero- one- and two-dimensional materialsnanostructures and nano-engineered devices with advanced performancenanobiotechnologynanomedicine and nanotoxicologyACS Nanoscience Au also publishes original experimental and theoretical research of an applied nature that integrates knowledge in the areas of materials engineering physics bioscience and chemistry into important applications of nanomaterials.
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