Porous Crystalline Olefin-Linked Covalent Organic Frameworks

The first unsubstituted olefin-linked covalent organic framework, termed COF-701, was made by linking 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4′-biphenyldicarbaldehyde (BPDA) through Aldol condensation. Formation of the unsubstituted olefin (-CH═CH-) linkage upon reticulation is confirmed by Fourier transform infrared (FT-IR) spectroscopy and solid-state 13 C cross-polarization magic angle spinning (CP-MAS) NMR spectroscopy of the framework and of its 13 C-isotope-labeled analogue. COF-701 is found to be porous (1715 m 2 g –1 ) and to retain its composition and crystallinity under both strongly acidic and basic conditions. The high chemical robustness is attributed to the unsubstituted olefin linkages. Immobilization of the strong Lewis acid BF 3 ·OEt 2 in the pores of the structure yields BF 3 ⊂COF-701. In the material, the catalytic activity of the guest is retained, as evidenced in a benchmark Diels–Alder reaction.