Molecular Orientation of a Nematic Liquid Crystal Induced by Mixing with Tetraalkylcalix[4]resorcinarenes at the Air–Water Interface

O-Octacarboxymethoxylated tetraalkylcalix[4]resorcinareanes (CRA-CMs) formed stable monolayers on a water surface, whereas their π-A isotherms were affected by the length of the alkyl residues. A double-layered structuring was observed for CRA-CM having four undecyl substituents (11CRA-CM) by compression, though CRA-CM with four eicosyl residues formed a stable monomolecular film. 11CRA-CM possessed the ability to form a host–guest monolayer film with liquid crystalline 4,4'-dihexylazobenzene at the air/water interface, leading to perpendicular orientation of C6Azo. The host–guest mixed monolayers displayed a double-layered structuring by compression.