Synthesis, functionalisation and post-synthetic modification of bismuth metal–organic frameworks

Abstract

Two new bismuth metal-organic frameworks (Bi-MOFs) were discovered using high throughput experiments employing bismuth(iii) nitrate pentahydrate and triazine-2,4,6-triyl-tribenzoic acid (HTATB). The reaction was carried out for long reaction times (∼5 d) in a water/DMF-mixture and resulted in the formation of [Bi(O)(OH)(TATB)]·HO (denoted as CAU-35). By switching to short reaction times and a methanol/DMF-mixture as the solvent, an analogue of CAU-7-BTB with the composition [Bi(TATB)]·DMF·6HO (denoted as CAU-7-TATB) was obtained. The use of the amino-functionalised HTATB linker (HTATB-NH) resulted in the formation of a functionalised porous Bi-MOF with the composition [Bi(TATB-NH)]·5HO·0.5DMF (CAU-7-TATB-NH). The structures of CAU-35 and CAU-7-TATB were successfully solved and refined from the PXRD data. CAU-7-TATB-NH was post-synthetically modified using anhydrides (acetic anhydride and valeric anhydride), cyclic anhydrides (succinic anhydride and phthalic anhydride), and 1,3-propane sultone. The degree of conversion ranged from 33% to 79%.

Bi(iii) MOFs: syntheses, structures and applications

“…The microwave synthesis applies microwave technology to make the chemicals inside the heated body perform a high-frequency reciprocating motion. [40][41][42] Unlike traditional heating, it has uniform heating, high efficiency and low energy consumption. In 2012, a porous and catalytically active material Bi(BTB) was successfully prepared by M. Feyand et al by either solvo- Hydrothermal method 1D Heterogeneous Catalytic thermal synthesis or microwave synthesis.…”

“…In K4, IBU is composed of BiNO 8 dimers with shared edges, which are connected into a one-dimensional chain and formed into a 3D structure by PTC 3 (CAU-7-TATB) were synthesized using a ligand and high-throughput method. 42 CAU-35 was solvothermally synthesized for 5 days in a H 2 O/DMF solution and CAU-7-TATB was prepared by the microwave method for 20 minutes in a CH 3 OH/DMF solution. The authors calculated and solved the structures of the two MOFs by PXRD data.…”

Synthesis, Transformation, Catalysis, and Gas Sorption Investigations on the Bismuth Metal–Organic Framework CAU‐17

“…Only four permanently microporous MOFs (i.e. type I isotherms for N 2 ) have been successfully synthesized using Bi 3+ cations, to the best of our knowledge, including CAU‐7, NOTT‐220, CAU‐17 and CAU‐35 . All of these MOFs have only been discovered within the past five years, and relatively few detailed analyses of their properties and their potential applications have been reported.…”

Metal–Organic Frameworks (MOFs) and Covalent Organic Frameworks (COFs) Applied to Photocatalytic Organic Transformations

“…Electron delocalization is enhanced in this type of COFs, since they are totally composed by Csp 2 -Csp 2 bonds [28]. Copyright (2013) American Chemical Society; Reference [31] Copyright (2014) American Chemical Society; Reference [32] Copyright (2015) American Chemical Society; References [33][34][35][36] Copyright (2019) American Chemical Society; References [37][38][39][40] with permission from John Wiley and Sons; References [41][42][43][44][45][46][47][48] with permission from The Royal Society of Chemistry; Reference [49] with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry; Reference [50] Published by the Royal Society of Chemistry; References [51,52] with permission from Elsevier. Copyright (2013) American Chemical Society; Reference [31] Copyright (2014) American Chemical Society; Reference [32] Copyright (2015) American Chemical Society; References [33][34][35][36] Copyright (2019) American Chemical Society; References [37][38][39][40] with permission from John Wiley and Sons; References [41][42][43][44][45][46][47][48] with permissio...…”