Held Philipp Alexander, Fuchs Harald, Studer Armido
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstraße 40, 48149, Münster, Germany.
Center for Nanotechnology, Heisenbergstraße 11, 48149, Münster, Germany.
Chemistry. 2017 May 2;23(25):5874-5892. doi: 10.1002/chem.201604047. Epub 2017 Jan 18.
In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field.
在这篇综述文章中，我们将讨论表面化学这一新兴研究领域的开创性工作和最新成果。表面化学，有时也被称为二维化学，在自下而上制备特定纳米结构方面显示出巨大潜力。与传统有机合成不同，传统有机合成反应通常在溶液中定义明确的反应烧瓶中进行，而表面化学是在超高真空条件下金属晶体上的扫描探针显微镜腔内进行的。金属首先作为有机构建块自组装的平台，在许多情况下，它还作为给定化学转化的催化剂。反应的产物以及反应的成功与否直接通过扫描探针显微镜进行分析。本综述对这种化学方法进行了总体概述，突出了与传统反应装置相比的优缺点。综述的第二部分则聚焦于已成功作为表面过程进行的反应。讨论了表面乌尔曼反应和格拉泽偶联反应。此外，还讨论了环脱氢反应和环加成反应，并重点介绍了涉及羰基官能团的反应。最后，考虑了连续表面化学的首个例子，其中两种不同的官能团被化学选择性地处理。这篇综述为该领域的专家提供了一个概述，同时也为非专家进入这个令人兴奋的新跨学科研究领域提供了一个起点。
