Defect formation and amorphization of Zn-MOF-74 crystals by post-synthetic interactions with bidentate adsorbates

Abstract

The controlled introduction of defects into MOFs is a powerful strategy to induce new physiochemical properties and improve their performance for target applications. Herein, we present a new strategy for...

Trapping of Photoluminescent Kinetic Intermediates During High-Concentration Synthesis of Non-Emissive Metal-Organic Frameworks

“…The H2dobdc 2− linker has been used to prepare a range of photoluminescent MOFs, which are generally proposed to emit via an excited state intramolecular proton transfer (ESIPT) pathway. [30][31][32]36,37,49,[63][64][65][66] Consistently, CORN-MOF-1 (Mg) fluoresces intensely upon irradiation with UV light in the solid state, whereas Mg2(dobdc) and H4dobdc emit only weakly (Figure 5). This initial observation demonstrates how subtle changes in MOF structure-stemming from a simple increase in the synthesis concentration-can significantly modulate MOF photophysical properties.…”

“…In addition, variations in solvent, temperature, metal precursor, and other synthesis parameters have been shown to produce a range of different Mg, [30][31][32][33][34][35][36] Mn, 37,38 Ni, 39 Co, [39][40][41][42] Cu, 26 and Zn [42][43][44][45][46][47][48] phases. Notably, some of these frameworks exhibit bright photoluminescence (PL) in the solid state, [30][31][32]36,37,49 whereas others are only weakly emissive, demonstrating that small changes in linker protonation state or spatial orientation can have a profound effect on framework photophysical properties. A critical barrier to predicting the preferred phase(s) is a lack of chemical insight into the processes underpinning M2(dobdc) self-assembly.…”

Trace to the Source: Self‐Tuning of MOF Photocatalysts

“…[ 338 ] The study of aMOFs is still in its infancy as there is no definitive knowledge of such transformation kinetics and specific transformation outcomes. [ 339 ] The preparation of aMOFs based on physical modulation (temperature, [ 340 ] pressure, [ 341 ] ball milling, [ 342 ] and electrical discharge [ 283 ] ) and chemical modulation (heterogeneous metals, [ 343 ] ligand competition, [ 344 ] solvents, [ 345 ] and modulators [ 346 ] ) is complicated. Moreover, in addition to the preparation difficulties, conventional crystallographic structural analysis methods are insufficient to study aMOFs.…”

Kinetic Trapping of Photoluminescent Frameworks During High-Concentration Synthesis of Nonemissive Metal–Organic Frameworks

“…In addition, variations in solvent, temperature, metal precursor, and other synthesis parameters have been shown to produce a range of different Mg, 29−35 Mn, 36,37 Ni, 38 Co, 38−41 Cu, 25 and Zn 41−47 phases. Notably, some of these frameworks exhibit detectable photoluminescence (PL) in the solid state, [29][30][31]35,36,48 demonstrating that small changes in the linker protonation state or spatial orientation can have a profound effect on framework photophysical properties. A critical barrier to predicting the preferred phase(s) is a lack of chemical insight into the processes underpinning M 2 (dobdc) self-assembly.…”