Molecular arrays formed in anisotropically rearranged supramolecular network with molecular substitutional asymmetry

We have designed two molecular building blocks, 2,6,11-tricarboxydecyloxy-3,7,10-triundecyloxy triphenylene (asym-TTT) and 2,6,10-tricarboxydecyloxy-3,7,11-triundecyloxy triphenylene (sym-TTT) with asymmetric and symmetric carboxyl groups, to construct distinct supramolecular networks. The supramolecular network of asym-TTT facilitates the formation of the directional-oriented molecular arrays of zinc phthalocyanines (ZnPc). The high-resolution scanning tunneling microscopic (STM) images as well as the density-functional theory (DFT) calculations reveal the preferential adsorption of ZnPc dimers in the anisotropic rearrangement of an asym-TTT supramolecular network. The self-repairing process of the molecular arrays after sweeping ZnPc dimers further confirms the anisotropic reconstruction of the asym-TTT network. The controlled experiments on the symmetrically substituted compound indicate the impact of the asymmetrically substituted carboxyl groups on the supramolecular networks.