Formation of Supramolecular Heterostacks at the Liquid-Solid Interface: Impact of Symmetry Mismatching on Structural Growth.

The construction of intricate three-dimensional (3D) nanoarchitectures on surfaces through molecular self-assembly attracts attention not only from a crystal engineering viewpoint but also because of its potential in a range of applications, given the current interest in van der Waals heterostructures. We herein report the formation of porous structures on alkane buffer layers on graphite. A dehydrobenzo[12]annulene (DBA) derivative having six decyloxy chains forms hexagonal structures on n -pentacontane and n -hexacontane buffer layers through van der Waals interactions at the 1-octanoic acid/graphite interface. The structural features are very similar to those on the graphite surface, except for the slight structural distortion, which is attributed to the p 2 symmetry of the buffer layer underneath. Moreover, based on the observation of small clusters of the DBA molecules, we discussed the nucleation and structural growth of the DBA network on a buffer layer. Finally, a hierarchical multicomponent structure was formed through the coadsorption of a heteromolecular cluster formed by a hydrogen-bonded isophthalic acid cyclic hexamer hosting a coronene molecule on the buffer layer. This study on supramolecular heterostacks provides insights into the construction of intricate 3D nanoarchitectures using self-assembly at interfaces.