Deprotonation-Induced Phase Evolutions in Co-Assembled Molecular Structures

In this work, we systematically studied the co-assembly behavior of 1,3,5-tris(4-carboxyphenyl)benzene (TCPB) and 4,4″-diamino-p-terphenyl (DATP) on a silver surface. Due to the thermal instability of carboxylic acids, the co-assembled structure exhibits temperature-dependent evolutions on Ag(111). The level of the deprotonation reactions of TCPB are clarified by the characteristic self-assembled footprints. Aided by these footprints, we are able to identify the structures of the complex co-assembly of TCPB and DATP entities at each stage. Finally, the conclusions are further evidenced by density functional theory calculations.