Photopolymerized two-dimensional organic films with calix[4]arene scaffold

• 2D covalent organic films of calix[4]arenes were created via Langmuir-Blodgett method. • Photoactive groups: naphthyls, chalcones and azides, were used for crosslinking. • Film thickness of 1–1.5 nm and wetting angles up to 100° were achieved. A series of 14 macromolecular derivatives of resorcinarenes and thiacalix[4]arenes bearing alkyl chains (up to -C 11 H 23 ) and different photoreactive groups (chalcone sulfonyl, naphthyl (Np), alkyl azide (Alk-N 3 )) was synthesized. The obtained compounds were used to design monomolecular 2D films by the Langmuir-Blodgett method at the air/water interface using ultraviolet-assisted covalent crosslinking. It was found that the alkyl azide derivatives can effectively form cross-copolymerized two-dimensional films with the thickness of 0.8-1.5 nm, which was revealed with the help of atomic force topography. A controversial effect of UV irradiation on the film topography, namely, ordering and disordering of the film structure, was observed. The effect of donor and acceptor substituents in styrene ring of chalcone sulfonyl (carbonyl) chlorides on the wetting angle of the films and its dependence on concentration of voids in a coating, were also studied. It was found that the most ordered 2D structures are formed for compounds with a sterically balanced set of substituents.