Selective and Competitive Adsorptions of Guest Molecules in Phase-Separated Networks

The formation of crystalline multicomponent 2D lattices, containing more than two different organic molecular building blocks, has been rarely achieved because optimized recognition and selection processes require us to achieve the targeted multicomponent surface confined patterns. In this Article, we show that tetraacidic azobenzene (NN4A) and 1,3,5-tris(10-carboxydecyloxy)-benzene (TCDB) molecules can exclusively form 2D phase-separated nanoporous networks via hydrogen bonds between carboxyl groups at the liquid-solid interface, which have two types of cavities with different size and symmetry. These networks can serve as organic templates for the accommodation of fullerene (C(60)), coronene, and copper(II) phthalocyanine (CuPc) molecules. The experimental and calculated results indicate that coronene can be immobilized in the cavities formed by both NN4A and TCDB, whereas CuPc can be immobilized only in the cavity formed by TCDB and C(60) can be immobilized only in the cavity formed by NN4A. Moreover, in the phase-separated networks, the coronene can be preferentially immobilized in NN4A. These results could benefit the studies on highly selectively molecular recognition and separation.