On-Surface Synthesis of Carbon-Based Scaffolds and Nanomaterials Using Terminal Alkynes

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• 作者：Florian Klappenberger ; Yi-Qi Zhang ; Jonas Bj枚rk ; Svetlana Klyatskaya ; Mario Ruben ; Johannes V. Barth
• 刊名：Accounts of Chemical Research
• 出版年：2015
• 出版时间：July 21, 2015
• 年：2015
• 卷：48
• 期：7
• 页码：2140-2150
• 全文大小：754K
• ISSN：1520-4898

文摘

The covalent linking of acetylene compounds is an important synthetic tool to control carbon鈥揷arbon bond formation and has been extensively studied for more than a century. Notably, Glaser coupling and subsequently developed refined procedures present an important route for the fabrication of distinct carbon-based scaffolds incorporating units with both sp²- and sp-hybridizations, such as carbyne chains, or two-dimensional (2D) graphyne or graphdiyne networks. However, the realization of the envisioned regular low-dimensional compounds and nanoarchitectures poses formidable challenges when following conventional synthesis protocols in solution, which we briefly overview. Now, recent developments in on-surface synthesis establish novel means for the construction of tailored covalent nanostructures under ultrahigh vacuum conditions. Here we focus on the exploration of pathways utilizing interfacial synthesis with terminal alkynes toward the atomically precise fabrication of low-dimensional carbon-rich scaffolds and nanomaterials. We review direct, molecular-level investigations, mainly relying on scanning probe microscopy, providing atomistic insights into thermally activated reaction schemes, their special pathways and products. Using custom-made molecular units, the employed homocoupling, cyclotrimerization, cycloaddition, and radical cyclization processes indeed yield distinct compounds, extended oligomers or 2D networks. Detailed insights into surface interactions such as bonding sites or conformational adaptation, and specific reaction mechanisms, including hierarchic pathways, were gained by sophisticated density functional theory calculations, complemented by X-ray spectroscopy measurements. For the fabrication of regular nanostructures and architectures, it is moreover imperative to cope with spurious side reactions, frequently resulting in chemical diversity. Accordingly, we highlight measures for increasing chemo- and regioselectivity by smart precursor design, substrate templating, and external stimuli. The ensuing preorganization of functional groups and control of side reactions increases product yields markedly. Finally, the electronic band structures of selected cases of novel low-dimensional hydrocarbon materials accessible with the monomers employed to date are discussed with a specific focus on their differences to theoretically established graphyne- and graphdiyne-related scaffolds. The presented methodology and gained insights herald further advancements in the field, heading toward novel molecular compounds, low-dimensional nanostructures, and coherently reticulated polymeric layers, eventually presenting well-defined arrangements with specific carbon鈥揷arbon bond sequencing and electronic characteristics. The functional properties of these or other foreseeable scaffolds and architectures bear significant prospects for a wide range of applications, for example, in nanoelectronics, photonics, or carbon-based technologies.