Boronate Covalent and Hybrid Organic Frameworks Featuring PIII and P=O Lewis Base Sites |
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Authors: | Piotr Pacholak Dr. Krzysztof Gontarczyk Dr. Radosław Kamiński Dr. Krzysztof Durka Prof. Sergiusz Luliński |
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Affiliation: | 1. Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland;2. Department of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089 Warsaw, Poland |
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Abstract: | 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. |
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Keywords: | coordination polymers covalent organic frameworks frustrated Lewis pairs quantum nature of host-guest interactions structural modeling |
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