Three-Dimensional Homochiral Covalent Organic Frameworks with Intrinsic Chiral qzd Topology.

ABSTRACT

Although a variety of chiral porous framework materials have been reported, there are few examples known to combine molecular chirality, helicity, and three-dimensional (3D) intrinsically chiral topology in one structure, which is beneficial for chirality transfer and amplification. Here, we report the synthesis of the first two 3D covalent organic frameworks (COFs) with an intrinsic chiral qzd topology, which exhibit unusual integration of various homochiral and homohelical features. By imine condensation of 4-connected porphyrin tetraamines and 2-connected enantiopure diene dialdehyde, we prepared two isostructural COFs with a noninterpenetrated qzd topology. The specific geometry and conformation flexibility of the V-shaped diene linker control the alignment of square-planar porphyrin units with rotational linkages and facilitate the creation of homochiral extended porous structures that feature a helical arrangement of porphyrins. Post-synthetic metalation of CCOF 23 with Rh(I) affords a heterogeneous catalyst for the asymmetric Michael addition reaction of aryl boronic acids to 2-cyclohexenone, which shows higher enantioselectivities compared to their homogeneous counterparts, presumably due to the confined effect of helical channels. This finding will provide an impetus to explore multichirality materials, offering new insights into the generation and control of helicity, homochirality, and enantioselectivity in the solid state.