Dynamic supramolecular assembly at the interface between a solution and a solid surface is a topic of growing importance in the self-assembly of molecular films and in developing theoretical descriptions of small molecule interactions. Organic building block design allows for a tremendous space of molecular design to be accessed, but also introduces many complex aspects of self-assembly, particularly with regard to the interplay of hierarchical intermolecular interactions. Subtle variations in these interactions, including interactions with the surface or solvent, can dramatically alter the self-assembled architectures. Here, we present several examples of these effects, including new results on macrocyclic molecules with peripheral functional groups designed to engage in complementary interactions. These systems are characterized by high-resolution scanning tunneling microscopy (STM) in the dynamic solution environment. We also discuss effects of host-guest supramolecular chemistry at the solution/solid interface where the guest plays a role in directing the assembly. Solvent co-adsorption has been shown to alter assembly structure and even the density of the surface packing. We will also discuss the dynamic behavior of ions within molecular receptor networks on surfaces. These can be manipulated by the bias voltage between the STM tip and the surface. Some of these systems exhibit the ability to template stacking into a film. We develop theoretical models to describe and interpret these results and to move us toward more predictive modeling. It is hoped that better understanding and control of these dynamic assembly effects will allow us to design and program next generation thin film materials.

Dynamic supramolecular assembly at surfaces: Impact of guest, solvent, and STM bias

254th National Meeting (2017)

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