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. Obtain...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-10, Vol.26 (56), p.12758-12768
Main Authors: Pacholak, Piotr, Gontarczyk, Krzysztof, Kamiński, Radosław, Durka, Krzysztof, Luliński, Sergiusz
Format: Article
Language:English
Subjects:
Boron
Carbon dioxide
Chemistry
Coordination
coordination polymers
Covalence
covalent organic frameworks
frustrated Lewis pairs
Lewis base
Phosphine
Phosphine oxide
Phosphorus
Polymers
quantum nature of host-guest interactions
Sorption
structural modeling
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Summary: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 Pd2dba3 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. The first boron‐phosphine covalent organic framework (BP‐COF) is reported, which can be considered as a new group of functional porous materials joining characteristics of frustrated Lewis pairs (FLPs) with enhanced sorption selectivity and solid‐state ligands for the coordination of transition‐metal atoms.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202001960