Tröger's Base Chemistry in Solution and in Zr(IV)-Based Metal-Organic Frameworks.
Wei GongMasoud Kazem-RostamiFlorencia A SonShengyi SuKira M FahyHaomiao XieTimur IslamogluYan LiuJ Fraser StoddartYong CuiOmar K FarhaPublished in: Journal of the American Chemical Society (2022)
Tröger's base (TB) and its derivatives have been studied extensively due to their unique concave shape stemming from the endomethylene strap. However, the strap-clipped TB chemistry has been largely overlooked in metal-organic framework (MOF) solids, leading to a gap in our knowledge within this field. In this work, we report the in situ strap elimination of a carboxylate-carrying TB in the presence of formic acid, both in solution and in Zr(IV)-based MOFs. In the solution system, the methanodiazocine nucleus can be exclusively transformed into an N , N' -diformyl-decorated phenhomazine derivative, regardless of the solvent used (DMF, DMA, or DEF), as unambiguously uncovered by single crystal X-ray crystallography. In contrast, while in the MOF synthetic system, the degree of derivatization reaction can be effectively controlled to give either the secondary diamine or formyl-decorated diamine, depending on the solvent used (DMF or DEF), resulting in the formation of two Zr-MOFs with 8-connected bcu (NU-1900) and 12-connected fcu (NU-407) topologies, respectively. The derivatization mechanism is proposed to be topology-guided and dependent on the local acid concentration during the MOF formation processes. Moreover, we discovered a novel post-synthetically water-induced in situ linker formylation process in NU-1900 through sequential formic acid elimination, migration, and condensation processes, affording an isostructural framework with the same linker as in NU-407, which further corroborates our proposed mechanism. Additionally, the highly defective NU-1900 with abundant accessible Zr sites was demonstrated to be an outstanding catalyst for the detoxification of a nerve agent simulant with a half-life of less than 1 min.
Keyphrases
- metal organic framework
- pet imaging
- mycobacterium tuberculosis
- ms ms
- solid state
- high performance liquid chromatography
- liquid chromatography tandem mass spectrometry
- simultaneous determination
- healthcare
- magnetic resonance
- gas chromatography mass spectrometry
- ionic liquid
- reduced graphene oxide
- quantum dots
- high resolution
- multidrug resistant
- magnetic resonance imaging
- liquid chromatography
- high glucose
- diabetic rats
- drug discovery
- solid phase extraction
- tandem mass spectrometry
- endothelial cells
- mass spectrometry
- gold nanoparticles
- room temperature
- peripheral nerve
- carbon dioxide
- structure activity relationship