Dative B←N bonds based crystalline organic framework with permanent porosity for acetylene storage and separation.

The utilization of dative B←N bonds for the creation of crystalline organic framework (BNOF) has increasingly received intensive interest; however, the shortage of permanent porosity is an obstacle that must be overcome to guarantee their application as porous materials. Here, we report the first microporous crystalline framework, BNOF-1, that is assembled through sole monomers, which can be scalably synthesized by the cheap 4-pyridine boronic acid. The 2D networks of BNOF-1 were stacked in parallel to generate a highly porous supramolecular open framework, which possessed not only the highest BET surface area of 1345 m 2 g -1 amongst all of the BNOFs but also features a record-high uptake of C 2 H 2 and CO 2 in covalent organic framework (COF) materials to date. Dynamic breakthrough experiments demonstrated that BNOF-1 material can efficiently separate C 2 H 2 /CO 2 mixtures. In addition, the network can be regenerated in organic solvents with no loss in performance, making its solution processable. We believe that BNOF-1 would greatly diversify the reticular chemistry and open new avenues for the application of BNOFs.