Symmetry propagation in surface supported supramolecular architectures of terpyridines and helicenes

The tunability of molecular self-assemblies together with the principles of supramolecular chemistry are the base of this thesis. In order to gain deeper insight into bigger bottom-up complexes like 3D metal organic frameworks (MOFs) or 2D hierarchical assemblies, we break down their dimensionality and complexity and monitor the on-surface self-organization behavior of the individual molecules.
In chapter [[1]] we introduce first on-surface results of a newly designed 4,2':6',4''-terpyridine. Its shape is specially designed to allow in-plane assemblies, in contrast to the ‘standard’ chelating 2,2':6',2''-terpyridines. We present nanoporous networks for both hydrogen bonded and metal coordinated assemblies, investigate their change in bonding and their adaptability to the surface reconstruction due to changed substrate interactions.
In chapter [[2]] we extend this study and try to answer the question how far can we scale up these simplified 2D investigations into the 3D world? Thereby we make use of an unique concept, by directly comparing the very same compounds in both cases: we compare the 2D self-organization in vacuum environment on Au(111) and Cu(111) surfaces and the role of Cu-adatoms with its in-solution counterparts comprising different Cu-salts and its resulting x-ray crystals. Beside this, due to utilization of different molecular functionalizations and external applied parameters, we further demonstrate the strength and tunability of such networks, and the influences even the smallest changes in the building block can exhibit on the large scale.
In chapter [[3]] we present another example of growth, namely 2D hierarchical with propagation of chirality. We investigate the chirality transfer from a single molecule over a hydrogen bonded trimer to an extended supramolecular assembly upon coordination. The latter is comprised of a trimeric structure of cobalt coordinated trimers hold together by weaker van der Waals forces. In this examination we employ both, enantiopure and racemic mixtures.