Abstract Metal–organic coordination structures are materials comprising reticular metal centers and organic linkers in which the two constituents bind with each other via metal–ligand coordination interaction. The underlying chemistry is more than a century old but has attracted tremendous attention in the last two decades owing to the rapidly development of metal–organic (or porous coordination) frameworks. These metal-coordination materials exhibit extraordinarily versatile topologies and many potential applications. Since 2002, this traditionally three-dimensional chemistry has been extended to two-dimensional space, that is, to synthesize metal–organic coordination structures directly on solid surfaces. This endeavor has made possible a wide range of so-called surface-confined metal–organic networks (SMONs) whose topology, composition, property and function can be tailored by applying the principle of rational design. The coordination chemistry manifests unique characteristics at the surfaces, and in turn the surfaces provide additional control for design structures and properties that are inaccessible in three-dimensional space. In this review, our goal is to comprehensively cover the progress made in the last 15 years in this rapidly developing field. The review summarizes (1) the experimental and theoretical techniques used in this field including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, density functional theory, and Monte Carlo and kinetic Monte Carlo simulation; (2) molecular ligands, metal atoms, substrates, and coordination motifs utilized for synthesizing SMON; (3) representative SMON structures with different topologies ranging from finite-size discrete clusters to one-dimensional chains, two-dimensional periodical frameworks and random networks; and (4) the properties and potential applications of SMONs. We conclude the review with some perspectives.

中文翻译：

---

表面金属有机配位结构的自组装

摘要 金属-有机配位结构是由网状金属中心和有机连接体组成的材料，其中两种成分通过金属-配体配位相互作用相互结合。基础化学已有一个多世纪的历史，但由于金属-有机（或多孔配位）框架的快速发展，在过去的二十年中引起了极大的关注。这些金属配位材料表现出极其通用的拓扑结构和许多潜在的应用。自 2002 年以来，这种传统的三维化学已扩展到二维空间，即直接在固体表面合成金属-有机配位结构。这项努力使广泛的所谓表面限制金属有机网络 (SMON) 成为可能，其拓扑、组成、属性和功能可以通过应用合理设计的原则来定制。配位化学在表面表现出独特的特性，反过来，表面为在三维空间中无法实现的设计结构和特性提供了额外的控制。在这次审查中，我们的目标是全面涵盖过去 15 年来在这个快速发展的领域取得的进展。综述总结了（1）该领域使用的实验和理论技术，包括扫描隧道显微镜和光谱学、低能电子衍射、X射线光电子能谱、X射线吸收光谱、密度泛函理论以及蒙特卡罗和动力学蒙特卡罗卡罗模拟；(2) 用于合成 SMON 的分子配体、金属原子、底物和配位基序；(3) 具有不同拓扑结构的代表性 SMON 结构，从有限大小的离散簇到一维链、二维周期框架和随机网络；(4) SMONs 的特性和潜在应用。我们以一些观点来结束评论。