Boronate Covalent and Hybrid Organic Frameworks Featuring PIII and P=O Lewis Base Sites.

Two covalent organic frameworks comprising Lewis basic PIII 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 cm3  g-1 at 1 bar at 77 K), methane (20 cm3  g-1 at 1 bar at 273 K) and carbon dioxide (50 cm3  g-1 at 1 bar at 273 K). They were exploited as solid-state ligands for coordination of Pd0 centers. Alternatively, in a bottom-up approach, boronated phosphine was treated with Pd2 dba3 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.