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

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(3)TATB). The reaction was carried out for long reaction times (similar to 5 d) in a water/DMF-mixture and resulted in the formation of [Bi-2(O)(OH)(TATB)]center dot H2O (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)]center dot DMF center dot 6H(2)O (denoted as CAU-7-TATB) was obtained. The use of the amino-functionalised H(3)TATB linker (H(3)TATB-NH2) resulted in the formation of a functionalised porous Bi-MOF with the composition [Bi(TATB-NH2)]center dot 5H(2)O center dot 0.5DMF (CAU-7-TATB-NH2). The structures of CAU-35 and CAU-7-TATB were successfully solved and refined from the PXRD data. CAU-7-TATB-NH2 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%.