摘要： The integration of molecules with irregular shape into a long-range, dense and periodic lattice represents a unique challenge for the fabrication of engineered molecular scale architectures. The tiling of pentagonal molecules on a 2D plane can be used as a proof-of-principle investigation to overcome this problem since basic geometry dictates that a two-dimensional (2D) surface cannot be filled with a periodic arrangement of pentagons, a fundamental limitation that suggests that pentagonal molecules may not be suitable as building blocks for dense films. However, here we show that the 2D covalent organic framework (COF) known as COF-1 can direct the growth of pentagonal guest molecules as dense crystalline films at the solution/solid interface. We find that the pentagonal molecule corannulene adsorbs at two different sites on the COF-1 lattice, and that multiple molecules can adsorb into well-defined clusters patterned by the COF. Two types of these dense periodic packing motifs lead to a five-fold symmetry reduction compatible with translational symmetry, one of which gives an unprecedented high molecular density of 2.12 molecules/nm2.