ABSTRACT
We report 9 crystal structures of a two-dimensional (2D) covalent organic framework (COF), including the parent Py-1P, 5 derivatives formed by chemical reactions, and 3 dynamic states by solvent exchange/loss. Structure details of these porous crystals, including stacking mode, interlayer distance, pore aperture, and incline angle, before, during, and after conversion processes in solution, were unveiled by single-crystal X-ray diffraction with resolutions up to 0.85 Å. The structure evolution is triggered by stepwise conformational transformation of the molecular building blocks in 2D COF, while their long-range ordering remained unsacrificed.
ABSTRACT
We report the construction of frustrated Lewis pairs (FLPs) in a metal-organic framework (MOF), where both Lewis acid (LA) and Lewis base (LB) are fixed to the backbone. The anchoring of a tritopic organoboron linker as LA and a monotopic linker as LB to separate metal oxide clusters in a tetrahedron geometry allows for the precise control of distance between them. As the type of monotopic LB linker varies, pyridine, phenol, aniline, and benzyl alcohol, a series of 11 FLPs were constructed to give fixed distances of 7.1, 5.5, 5.4, and 4.8 Å, respectively, revealed by 11B-1H solid-state nuclear magnetic resonance spectroscopy. Keeping LA and LB apart by a fixed distance makes it possible to investigate the electrostatic effect by changing the functional groups in the monotopic LB linker, while the LA counterpart remains unaffected. This approach offers new chemical environments of the active site for FLP-induced catalysis.
