This talk will analyse the effect of an inorganic surface on the spontaneous organisation of molecular building blocks into complex architectures by considering forces between molecules and surfaces as a further ingredient in the complex hierarchy of interactions that govern supramolecular self-assembly. It will be shown that while surfaces clearly introduce bring an extra degree of complexity into this already intricate problem, they also represent a unique opportunity for understanding the fundamental processes at play because of the availability of extremely high resolution analytical techniques that allow to investigate and even visualise the assemblies down to the molecular and atomic scale.<br/>A number of recent examples drawn from the collaboration between our laboratory and several theoretical groups will be presented, exemplifying cases where the surface has different degrees of influence. We will start from the instance where the effect of the surface is minimal, demonstrating that two-dimensional (2D) hierarchical supramolecular nanostructures can be programmed by molecular design. We will then move to the case when the substrate templating effect becomes more relevant, presenting recent efforts to develop a general, though simple and computationally inexpensive model with quantitative predictive capabilities, providing a comprehensive description of the ‘subtle interplay’ between intermolecular and molecule-substrate interactions. Finally, we will deal with the question of how far the surface templating effect extends when moving from 2D to thin film growth, demonstrating that the answer critically depends on the differences between the monolayer and the molecular bulk crystalline structure. This last topic will also be used to discuss the importance of expanding our current, traditional surface science experimental techniques in order to analyse molecular films beyond the ultra-thin monolayer limit.

Hierarchy of interactions and templation effects in supramolecular assembly at surface: From organic monolayers to thin films

253rd National Meeting (2017)

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