ICMADS (In-situ Chemistry of Molecular Assemblies on Dielectric Surfaces)

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Recently, the concept of on-surface chemistry has been exploited for fabrication of functional molecular structures. This approach opens up the possibility for creating thermally and chemically stable structures that cannot be achieved by standard deposition and assembly techniques. Moreover, confining the reaction in two dimensions may enable new reaction routes that are not accessible in solution. Published experiments involving on-surface chemistry have been limited to metallic surfaces so far, or in one recent example on a monolayer of NaCl/Ag(100). In this project we will explore on-surface chemistry for creating molecular structures on dielectric surfaces. Two fundamentally different strategies for on-surface chemistry will be investigated on two model surfaces, namely calcium fluoride and calcite. First, we will explore the formation of extended structures by metal-complexation upon co-adsorption of diacids, triacids or polyazaaromatics and metal atoms. Second, we will induce covalent coupling of radicals obtained by in-situ heterolytic thermal cleavage of molecules such as iodoaromatics and by esterification of di- and triboronic acids with alpha-diiols. The project includes the design and synthesis of tailor-made molecules, their activation and a detailed surface and molecular characterisation by direct imaging using variable-temperature non-contact scanning force microscopy as well as ultraviolet photoelectron and metastable impact electron spectroscopy. Simulations will be performed for gaining insights into the molecular structures and to confirm reaction pathways.