The precise localization of organic molecules in controllable positions is an important step towards constructing functional nanostructures via the bottom-up strategy. Herein, supramolecularly organized C70-fullerene assemblies on macrocycle-modified surfaces were investigated using scanning tunneling microscopy (STM) in combination with theoretical calculations. The results revealed that an up-assembly of C70-fullerene adlayers was successfully formed on top of the bottom macrocycle arrays. Density functional theory (DFT) calculations confirmed that the macrocycle networks along with the co-adsorbed solvent 1-phenyloctane served as a selective template for trapping C70-fullerene molecules in the spectral sites and acted as a support for the C70-fullerene molecules. The periodical distribution of the C70-fullerene molecules should facilitate understanding of the strong dependence of the arrangement of C70-fullerene upon the specific interactions (apart from spatial recognition) derived from modification of the sub-monolayers.

The precise control of the conformations of biomolecules adsorbed on a surface at the single-molecule level is significant. However, it remains a huge challenge because of the complex structure and conformation diversity of biomolecules. Herein, a "nanopore-confined recognition" strategy is proposed to manipulate the adsorption of individual valinomycin molecules at room temperature through precise design of functionalized conjugated macrocycle (CPN8) supramolecular nanopores with complementary architectures and binding sites. We revealed that CPN8 prefers to selectively recognizing valinomycin with complementary architecture because of the strong synergistic interactions between the isopropyl groups of valinomycin and the amino groups of CPN8, with valinomycinhighly oriented pyrolytic graphite (HOPG) interactions. Our perspectives at the single-molecule level will provide valuable insights to improve the design of supramolecular nanopores for conformation-selective recognition of non-conjugated molecules.