To demonstrate key roles of multiple interactions between multiple components and multiple phases in the formation of an uncommon self-assembling pattern, we present here the construction of a porous hexagonal star (h-star) structure using a trigonal molecular building block at the liquid/solid interface. For this purpose, self-assembly of hexaalkoxy-substituted dehydrobenzo[12]annulene derivatives DBA-OCns was investigated at the tetradecane/graphite interface by means of scanning tunneling microscopy (STM). Monolayer structures were significantly influenced by coadsorbed tetradecane molecules depending on the alkyl chains length (C13-C16) of DBA-OCn. However, none of DBA-OCn molecules formed the expected trigonal complexes, indicating that an additional driving force is necessary for the formation of the trigonal complex and its assembly into the h-star structure. As a first approach, we employed the "guest induced structural change" for the formation of the h-star structure. In the presence of two guest molecules, nonsubstituted DBA and hexakis(phenylethynyl)benzene which fit the respective pores, an h-star structure was formed by DBA-OC15 at the tetradecane/graphite interface. Moreover, a tetradecane molecule was coadsorbed between a pair of alkyl chains of DBA-OC15, thereby blocking the interdigitation of the alkyl chain pairs. Therefore, the h-star structure results from the self-assembly of the four molecular components including the solvent molecule. The second approach is based on aggregation of perfluoroalkyl chains via fluorophilicity of DBA-F, in which the perfluoroalkyl groups are substituted at the end of three alkyl chains of DBA-OCn via p-phenylene linkers. A trigonal complex consisting of DBA-F and three tetradecane molecules formed an h-star structure, in which the perfluoroalkyl groups that orient into the alkane solution phase aggregated at the hexagonal pore via fluorophilicity. The present result provides useful insight into the design and control of complex molecular self-assembly at the liquid/solid interface.

An approach to synthesize a two‐dimensional polymer (2DP) using a preorganized host‐guest network at the liquid/solid interface is presented. As a host network, we used a self‐assembled monolayer of a dehydrobenzo[12]annulene derivative having aminophenyl groups at three alkoxy chain ends and, as a guest, a hexakis(phenylethynyl)benzene derivative having six formyl groups, aiming to connect the host to the guest embedded in the host matrix by imine bond formation. STM observations of host‐guest mixtures with trifluoroacetic acid at the 1‐phenyloctane/highly oriented pyrolytic graphite interface revealed that the guest was observed as a spoke‐like feature in the nanowells. Based on the STM image analysis, short distances between the diagonal phenyl groups in the nanowells are detected, indicating that the imine bonds are formed. However, the small abundance and random distribution of the short phenyl‐phenyl distance indicate that the periodically ordered 2DP structure is not formed, probably because the network cannot tolerate the structural change due to partial bond formation.