Boronate Covalent and Hybrid Organic Frameworks Featuring P(III) and P=O Lewis Base Sites

Two covalent organic frameworks comprising Lewis basic P(III) centers and Lewis acidic boron atoms were prepared by poly‐condensation reactions of newly obtained tris(4‐diisopropoxyborylphenyl)phosphine with 2,3,6,7,10,11‐hexahydroxytriphenylene and 2,3,6,7‐tetrahydroxy‐9,10‐dimethylanthracene. Obtained materials exhibit significant sorption of dihydrogen (100 cm(3) g(−1) at 1 bar at 77 K), methane (20 cm(3) g(−1) at 1 bar at 273 K) and carbon dioxide (50 cm(3) g(−1) at 1 bar at 273 K). They were exploited as solid‐state ligands for coordination of Pd(0) centers. Alternatively, in a bottom‐up approach, boronated phosphine was treated with Pd(2)dba(3) and poly‐condensated, yielding hybrid materials where the polymer networks are formed by means of covalent boronate linkages and coordination P−Pd bonds. In addition, the analogous materials based on phosphine oxide were synthesized. The DFT calculations on framework–guest interactions revealed that the behavior of adjacent boron and phosphorus/phosphine oxide centers is reminiscent of that found in Frustrated Lewis Pairs and may improve sorption of selected molecules.