Exploring On-Surface Synthesis under Mild Conditions.

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Yi-Qi Zhang,Jonas Björk,Johannes V Barth
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引用次数: 0

Abstract

ConspectusBottom-up approaches combining tailor-made molecular precursors and surface-mediated reactions under ultrahigh-vacuum (UHV) conditions attracted significant attention over the past decade as a promising strategy for synthesizing novel, functional, molecule-based materials. These methods have been remarkably successful in creating unconventional covalent products with atomic precision, though largely focusing on one-dimensional (1D) polymeric products. Extending the established protocols to synthesize two-dimensional (2D) covalent architectures presents a major challenge, primarily due to high annealing temperatures required that often entail competing reactions, high defect densities, and structural degradation.In this Account, we highlight the exciting potential of low-temperature (LT) on-surface reactions as an alternative pathway and discuss their largely unexploited capabilities. We summarize major recent advances, focusing on coinage metal surface-assisted chemical transformations at mild conditions in UHV, proceeding frequently near or below room temperature (RT). Special emphasis is placed on alkyne derivatives, either alone or combined with other functional groups, identified as versatile building blocks for next-generation carbon-rich nanomaterials such as graphyne or graphdiyne and their metalated derivatives, which offer immense potential for future technological applications.We discuss four major pathways for initiating LT on-surface reactions of alkyne species, following largely the chronological order of their discovery, and merging insights from high-resolution scanning probe microscopy, X-ray spectroscopies and density functional theory calculations: (i) Conversions catalyzed by in situ generated species and extrinsic elements; (ii) quantum tunneling-mediated reactions; (iii) reaction pathways involving surface-assisted radical or hydrogen transfer processes; and (iv) gas-mediated on-surface reactions. These and other selected examples of LT synthesis protocols offer significant advantages in terms of high selectivity and efficiency, notably enabling the controlled synthesis of extended, regular 2D organometallic and covalent compounds or architectures, and bearing promise for a multitude of all-carbon scaffolds, which currently remain challenging. We aim to inspire the development of functional robust nanoarchitectures with long-range order and atomic-scale precision, contributing to the advancement of molecule-based materials for diverse technological applications.
温和条件下的表面合成探索。
自底向上的方法结合了定制的分子前体和在超高真空(UHV)条件下的表面介导反应,在过去十年中作为一种有前途的合成新型功能分子基材料的策略引起了极大的关注。这些方法在制造具有原子精度的非常规共价产物方面非常成功,尽管主要集中在一维(1D)聚合物产物上。将已建立的协议扩展到合成二维(2D)共价结构提出了主要挑战,主要是由于需要高退火温度,通常需要竞争性反应,高缺陷密度和结构降解。在这篇文章中,我们强调了低温(LT)表面反应作为一种替代途径的令人兴奋的潜力,并讨论了它们在很大程度上尚未开发的能力。我们总结了最近的主要进展,重点是在特高压温和条件下,在接近或低于室温(RT)的情况下进行金属表面辅助化学转化。特别强调的是炔衍生物,无论是单独还是与其他官能团结合,被确定为下一代富碳纳米材料的通用构建模块,如石墨炔或石墨炔及其金属化衍生物,为未来的技术应用提供了巨大的潜力。我们讨论了四种引发炔类表面LT反应的主要途径,主要是根据它们发现的时间顺序,并结合高分辨率扫描探针显微镜、x射线光谱和密度泛函理论计算的见解:(i)由原位生成的物质和外来元素催化的转化;(ii)量子隧道介导的反应;(iii)涉及表面辅助自由基或氢转移过程的反应途径;(iv)气体介导的表面反应。这些和其他选择的LT合成方案的例子在高选择性和效率方面提供了显着的优势,特别是能够控制合成扩展的,规则的二维有机金属和共价化合物或结构,并为大量的全碳支架提供了希望,这目前仍然具有挑战性。我们的目标是激发具有远程有序和原子尺度精度的功能健壮的纳米结构的发展,为分子基材料的各种技术应用的进步做出贡献。
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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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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