Lin Nian, Stepanow Sebastian, Ruben Mario, Barth Johannes V
Department of Physics, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, P.R. China,
Top Curr Chem. 2009;287:1-44. doi: 10.1007/128_2008_150.
The non-covalent synthesis of coordination compounds and networks provides promising avenues towardsmetal-containing supermolecules and nanostructured materials with ultimate feature definition. An importantfactor for their further development, and their integration and exploitation in nanoscale functional systems,is the capability to prepare or organize them at well-defined substrates or templated environments. Supramolecularengineering on atomistically controlled surfaces has been propelled by the direct insight into low-dimensionalcoordination systems provided by scanning tunneling microscopy observations. Here we discuss the principlesof surface-confined supramolecular coordination chemistry, emphasizingself-assembly protocols conducted on surface atomic lattices employing metal centers to direct the organizationof molecular ligands and the template-induced organization of prefabricated metallosupramolecular species.The presented exemplary molecular-level studies elucidate the arrangement of organic adsorbates and transitionmetal adatoms on low-index metal and graphite surfaces. They reveal the interplay between molecule-adatom,intermolecular, and adsorbate-substrate interactions, which need to be balanced for the fabricationof low-dimensional nanostructures. The control and understanding of both the nature of metal-ligandinteractions and the resulting supramolecular organization on solid surfaces is decisive for the designof advanced architectures with concomitant functions. The realized metallosupramolecular compounds andarrays combine the properties of their constituent metal ions and organic ligands, and feature versatilestructural characteristics as well as attractive functional aspects: their redox, magnetic, spin-state,and electronic transitions.
配位化合物和网络的非共价合成提供了通往具有最终特征定义的含金属超分子和纳米结构材料的有前景的途径。它们进一步发展以及在纳米级功能系统中的整合与应用的一个重要因素是在明确界定的底物或模板环境中制备或组织它们的能力。对扫描隧道显微镜观察所提供的低维配位系统的直接洞察推动了原子尺度可控表面上的超分子工程。在此，我们讨论表面受限超分子配位化学的原理，重点强调在表面原子晶格上进行的自组装方案，利用金属中心来指导分子配体的组织以及预制金属超分子物种的模板诱导组织。所展示的示例性分子水平研究阐明了有机吸附质和过渡金属吸附原子在低指数金属和石墨表面上的排列。它们揭示了分子 - 吸附原子、分子间以及吸附质 - 底物相互作用之间的相互作用，对于制造低维纳米结构而言，这些相互作用需要达到平衡。对金属 - 配体相互作用的性质以及在固体表面上由此产生的超分子组织的控制和理解对于设计具有伴随功能的先进结构至关重要。所实现的金属超分子化合物和阵列结合了其组成金属离子和有机配体的性质，并具有多样的结构特征以及吸引人的功能方面：它们的氧化还原、磁性、自旋态和电子跃迁。
