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Boronate Covalent and Hybrid Organic Frameworks Featuring P III and P=O Lewis Base Sites
Author(s) -
Pacholak Piotr,
Gontarczyk Krzysztof,
Kamiński Radosław,
Durka Krzysztof,
Luliński Sergiusz
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001960
Subject(s) - frustrated lewis pair , lewis acids and bases , phosphine oxide , phosphine , covalent bond , sorption , chemistry , polymer chemistry , boron , inorganic chemistry , organic chemistry , catalysis , adsorption
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.