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BN‐doped metal–organic frameworks: tailoring 2D and 3D porous architectures through molecular editing of borazines

Fasano, Francesco, Dosso, Jacopo, Bezzu, C. Grazia, Carta, Mariolino, Kerff, François, Demitri, Nicola, Su, Bao-Lian and Bonifazi, Davide 2021. BN‐doped metal–organic frameworks: tailoring 2D and 3D porous architectures through molecular editing of borazines. Chemistry - A European Journal 27 (12) , pp. 4124-4133. 10.1002/chem.202004640

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Building on the MOF approach to prepare porous materials, herein we report the engineering of porous BN‐doped materials using tricarboxylic hexaarylborazine ligands, which are laterally decorated with functional groups at the full‐carbon ‘inner shell’. Whilst an open porous 3D entangled structure could be obtained from the double interpenetration of two identical metal frameworks derived from the methyl substituted borazine, the chlorine‐functionalised linker undergoes formation of a porous layered 2D honeycomb structure, as shown by single‐crystal X‐ray diffraction analysis. In this architecture, the borazine cores are rotated by 60° in alternating layers, thus generating large rhombohedral channels running perpendicular to the planes of the networks. An analogous unsubstituted full‐carbon metal framework was synthesised for comparison. The resulting MOF revealed a crystalline 3D entangled porous structure, composed by three mutually interpenetrating networks, hence denser than those obtained from the borazine linkers. Their microporosity and CO2 uptake were investigated, with the porous 3D BN‐MOF entangled structure exhibiting a large apparent BET specific surface area (1091 m2 g−1) and significant CO2 reversible adsorption (3.31 mmol g−1) at 1 bar and 273 K.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Additional Information: This is an open access article under the terms of the Creative Commons Attribution License
Publisher: Wiley
ISSN: 0947-6539
Funders: EU through the MSCA-RISE funding scheme (project INFUSION)
Date of First Compliant Deposit: 2 February 2021
Date of Acceptance: 30 November 2020
Last Modified: 25 May 2021 01:30

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