Actinide‐Based Porphyrinic MOF as a Dehydrogenation Catalyst

Abstract

Uranyl-organic frameworks (UOFs) have recently been the object of many research endeavors due to the unique coordination mode of uranyl ions and their attractive physicochemical properties. Here, a new (3,4)-connected UOF (U-IHEP-4) assembled from uranyl and porphyrin ligand tetrakis(4-carboxyphenyl)porphyrin (H4TCPP) is reported, which represents the first case of actinide porphyrinic MOFs. Adsorption experiments in DMF solution demonstrated that U-IHEP-4 selectively adsorbs positively charged dyes, which is in line with its negatively charged framework and large pore volume ratio (90 %). Remarkably, U-IHEP-4 exhibited high catalytic activity for the dehydrogenation of N-heterocycles to synthesize the corresponding aromatic heterocycles and it can be used as an efficient heterogeneous catalyst.

Beyond structural motifs: the frontier of actinide-containing metal–organic frameworks

“…For example, there are very few types of reactions ( e.g. , cycloaddition, dehydrogenation, and photocatalytic oxidation) 57,273–276 that have been probed so far on An-MOFs as heterogeneous catalysts. As a result, there are even fewer reports focused on mechanistic studies of catalytic transformations occurring in An-based MOFs.…”

“… 274,275 For example, a U-MOF with integrated porphyrin-based linkers, Co-TCPP (Co-TCPP = Co( ii ) tetra(4-carboxyphenyl) porphyrin) was used for catalyzing N-heterocycle dehydrogenation reactions. 57 Specifically, dehydration of nine different N-heterocyclic compounds ( e.g. , 1,2,3,4-tetrahydroquinoline to quinoline) occurred at yields ranging from 61–98%.…”

Viologen‐Based Uranyl Coordination Polymers: Anion‐Induced Structural Diversity and the Potential as a Fluorescent Probe

“…U-IHEP-4 shows high catalytic activity for the dehydrogenation of N-heterocycles. [6] U-IHEP-9 acts as a heterogeneous photocatalyst for CO 2 cycloaddition under the driving of visible light at room temperature. [7] Wang's group reported a uranyl MOC (metalorganic cage) based on a sulfur-containing bidentate carboxylic ligand, [8] which can effectively convert X-ray photons to electrical current signals and presents a promising sensitivity of 54.93 μC • Gy À 1 • cm À 2 .…”

Uranyl Ion Complexes of Polycarboxylates: Steps towards Isolated Photoactive Cavities

“…Selectivity of these reactions has not been a major focus and in some early instances [34] would be expected to have been determined by the nature of the preformed support upon which uranyl centres were immobilised. Given that the use of a radioactive material would pose problems in any large-scale application for environmental remediation or water splitting, an alternative, more appealing prospect is that of selective photochemical synthesis within cavities of a porous uranyl complex crystal, a prospect which parallels what has already been realised for synthesis in general with other metal ion derivatives [2,[36][37][38] and which is rendered worthy of wider investigation by the observation of selective incorporation of various materials into the cavities of some known uranyl ion coordination polymers [39][40][41][42][43][44][45].…”