Rational design of crystalline two-dimensional frameworks with highly complicated topological structures

Constructing two-dimensional (2D) polymers with complex tessellation patterns via synthetic chemistry makes a significant contribution not only to the understanding of the emergence of complex hierarchical systems in living organisms, but also to the fabrication of advanced hierarchical materials. However, to achieve such tasks is a great challenge. In this communication we report a facile and general approach to tessellate 2D covalent organic frameworks (COFs) by three or four geometric shapes/sizes, which affords 2D COFs bearing three or four different kinds of pores and increases structural complexity in tessellations of 2D polymers to a much higher level. The complex tessellation patterns of the COFs are elucidated by powder X-ray diffraction studies, theoretical simulations and high-resolution TEM.