Boronate Covalent and Hybrid Organic Frameworks Featuring PIII and P=O Lewis Base Sites. Issue 56 (1st September 2020)

• Record Type: Journal Article
• Authors: Pacholak, Piotr; Gontarczyk, Krzysztof; Kamiński, Radosław; Durka, Krzysztof; Luliński, Sergiusz
• Is Part Of: Chemistry. Volume 26:Issue 56(2020)
• Page Start: 12758
• Page End: 12768
• Publication Date: 2020-09-01
• Subjects: coordination polymers -- covalent organic frameworks -- frustrated Lewis pairs -- quantum nature of host-guest interactions -- structural modeling; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202001960
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 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. Abstract : 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.