(438a) Investigating How Entropy Compartmentalization Drives the Formation of Robust Host-Guest Structures

Host–Guest systems have recently shown promise for the assembly of open colloidal structures. Such open structures are promising because they offer novel photonic and photonic properties. Understanding how particle shape drives this assembly is key because, for hard particles, shape controls what structures form. In this work, we theoretically explain how shape alone controls the formation of 2D host guest structures, as well as the potential application of such structures for adsorption. First, we show that the assembly of Host Guest structures is possible with hard star particles as hosts and rectangles or squares as guests. We then use a free volume mean field theory to show that guest particles contribute significantly more to the entropy of the system, thereby providing evidence of what we call ’entropy compartmentalization’ as the driving mechanism for assembly. Such compartmentalization, where guest particles have more free area and are orientationally free, while host particles are orientationally locked, is confirmed by analysis of the average host and guest orientation distributions and mean squared displacements. Finally, we show that assembly is robust to host shape perturbation and that the structures that adsorption of hard particles to the host structures can be modelled via a Langmuir isotherm.