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

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 46; no. 26; pp. 8658 - 8663
• Main Authors: Köppen, M, Beyer, O, Wuttke, S, Lüning, U, Stock, N
• Format: Journal Article
• Language: English
• Published: England 04.07.2017
• Subjects: Anhydrides; Bismuth; Conversion; Formations; Metal-organic frameworks; Methyl alcohol; Reaction time; Solvents
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c7dt01744h

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 (H TATB). 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)]·H O (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·6H O (denoted as CAU-7-TATB) was obtained. The use of the amino-functionalised H TATB linker (H TATB-NH ) resulted in the formation of a functionalised porous Bi-MOF with the composition [Bi(TATB-NH )]·5H O·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%.