Metal–Organic Framework Seeding to Drive Phase Selection and Overcome Synthesis Limitations

Bois, Derek R. Du; Matzger, Adam J.

doi:10.1021/acs.cgd.2c00762

Cited by 7 publications

(27 citation statements)

References 22 publications

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“…In particular, the need for liters of solvent(s) and disproportionate quantities of acid modulators often limit MOF synthesis to sub-gram quantities. Recently, Matzger and coworkers, 137 along with our group, 138 have found that much higher reaction concentrations (up 1 M in some cases) can be used to produce high-quality MOFs with significantly reduced solvent waste. In a similar vein, we carried out a structure-property study to identify the optimal modulator for Zr-MOF synthesis, with the goal of reducing the amount of modulator required to produce highly crystalline material.…”

Section: Robustness Of Mofs For Organic Synthesismentioning

confidence: 99%

MOFganic Chemistry: Challenges and Opportunities for Metal-Organic Frameworks in Synthetic Organic Chemistry

Ahmad

Keasler

Stacy

et al. 2023

Preprint

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Metal-organic frameworks (MOFs) are porous, crystalline solids constructed from organic linkers and inorganic nodes that have been widely studied for applications in gas storage, chemical separations, and drug delivery. Owing to their highly modular structures and tunable pore environments, we propose that MOFs have significant untapped potential as catalysts and reagents relevant to the synthesis of next-generation therapeutics. Herein, we outline the properties of MOFs that make them promising for applications in synthetic and organic chemistry, including new reactivity and selectivity, enhanced robustness, and user-friendly preparation. In addition, we outline the challenges facing the field and propose new directions to maximize the utility of MOFs for drug synthesis. This perspective aims to bring together the organic and MOF communities to develop new heterogeneous platforms capable of achieving synthetic transformations that can-not be replicated by homogeneous systems.

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Section: Robustness Of Mofs For Organic Synthesismentioning

confidence: 99%

MOFganic Chemistry: Challenges and Opportunities for Metal-Organic Frameworks in Synthetic Organic Chemistry

Ahmad

Keasler

Stacy

et al. 2023

Preprint

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“…8 Unfortunately, the large solvent volumes required for traditional solvothermal synthesis necessitate the use of liters of solvent to produce sub-gram quantities of MOF, contributing greatly to the cost of MOFs on scale and generating significant waste. 11 Solvothermal MOF syntheses at higher concentrations are rare, [12][13][14][15][16] as poorly crystalline or low surface area materials are typically isolated instead due to the rapid precipitation of products from solution. 13,[17][18][19][20][21] The MOF-74, CPO-27, or M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd; dobdc 4− = 2,5-dioxido-1,4-benzenedicarboxylate) family of frameworks embodies the aforementioned synthetic challenges (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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

Halder

Bain

Pitt

et al. 2023

Preprint

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Metal-organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes with potential utility in gas separations, drug delivery, sensing, and catalysis. Small variations in MOF synthesis conditions can lead to a range of accessible frameworks with divergent chemical or photophysical properties. New meth-ods to controllably access phases with tailored properties would broaden the scope of MOFs that can be reliably prepared for specific applications. Herein, we demonstrate that simply increasing the reaction concentration during the solvother-mal synthesis of M2(dobdc) (M = Mg, Mn, Ni; dobdc4− = 2,5-dioxido-1,4-benzenedicarboxylate), also known as MOF-74, unexpectedly leads to trapping of a kinetic intermediate termed CORN-MOF-1 (CORN = Cornell University). In-depth spec-troscopic, crystallographic, and computational studies support that CORN-MOF-1 has a similar structure to M2(dobdc) but with partially protonated linkers and charge-balancing or coordinated formate groups in the pores. The resultant vari-ation in linker spacings causes CORN-MOF-1 (Mg) to be strongly photoluminescent in the solid state, whereas H4dobdc and Mg2(dobdc) are weakly emissive due to excimer formation. In addition, CORN-MOF-1 variants can be converted into high-quality samples of the thermodynamic M2(dobdc) phases by heating in N,N-dimethylformamide (DMF). Overall, our findings support that high-concentration synthesis provides a straightforward method to identify new kinetic MOF phas-es with different properties from known materials and to produce highly porous samples of MOFs, paving the way for the discovery and gram-scale synthesis of framework materials.

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“…A more user-friendly approach would be to simply conduct solvothermal synthesis at much higher reaction concentrations (e.g., 1.00 M, an approximately 100-fold increase). 10,11 However, examples of successful MOF syntheses even at intermediate concentrations (0.15-0.25 M) remain surprisingly scarce; 10,[12][13][14] more common instead are reports of poorly crystalline products, unusual morphologies, low surface area materials, or different phases forming at high concentrations due to the rapid precipitation of products from solution. 10,11,[15][16][17][18] These findings beg the question: can MOFs effectively self-assemble at high reaction concentrations?…”

Section: Introductionmentioning

confidence: 99%

“…10,11 However, examples of successful MOF syntheses even at intermediate concentrations (0.15-0.25 M) remain surprisingly scarce; 10,[12][13][14] more common instead are reports of poorly crystalline products, unusual morphologies, low surface area materials, or different phases forming at high concentrations due to the rapid precipitation of products from solution. 10,11,[15][16][17][18] These findings beg the question: can MOFs effectively self-assemble at high reaction concentrations? MOFs constructed from Zr6 nodes (Zr-MOFs), [19][20][21] as well as isostructural Hf-based MOFs (Hf-MOFs), 22 exemplify the challenges and opportunities associated with high-concen-tration MOF synthesis.…”

Section: Introductionmentioning

confidence: 99%

“…The MOFs produced by mechanochemical synthesis also vary in crystallinity, with broad powder X-ray diffraction (PXRD) reflections indicative of small crystalline domain sizes in many cases. [31][32][33] On the other hand, the high-concentration solvothermal synthesis of UiO-66 (~0.45 M) has only been achieved when the reaction mixture was seeded with pre-synthesized MOF, 10 and successful high-concentration synthesis (>0.25 M) has yet to be reported for any other Zr-or Hf-MOF. Herein, we demonstrate that high-quality Zr-and Hf-MOFs can be generally synthesized at high reaction concentrations, up to 1.00 M in linker in many cases, using either simple metal chloride salts or well-defined pivalate-capped cluster precursors.…”

Section: Introductionmentioning

confidence: 99%

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High-Concentration Self-Assembly of Zirconium- and Hafnium-Based Metal-Organic Materials

Jerozal

Pitt

MacMillan

et al. 2023

Preprint

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Metal–organic frameworks (MOFs) are crystalline, porous solids constructed from organic linkers and inorganic nodes that are promising for applications in chemical separations, gas storage, and catalysis, among many others. However, a major roadblock to the widespread implementation of MOFs, including highly tunable and hydrolytically stable Zr- and Hf-based frameworks, is their benchtop-scalable synthesis, as MOFs are typically prepared under highly dilute (≤0.01 M) solvothermal conditions. This necessitates the use of liters of organic solvent to prepare only a few grams of MOF. Here-in, we demonstrate that Zr- and Hf-based frameworks (eight examples) can self-assemble at much higher reaction concen-trations than are typically utilized, up to 1.00 M in many cases. Combining stoichiometric amounts of Zr or Hf precursors with organic linkers at high concentrations yields highly crystalline and porous MOFs, as confirmed by powder X-ray diffraction (PXRD) and 77 K N2 surface area measurements. Further, the use of well-defined pivalate-capped cluster pre-cursors avoids the formation of ordered defects and impurities that arise from standard metal chloride salts. These clus-ters also introduce pivalate defects that increase the exterior hydrophobicity of several MOFs, as confirmed by water con-tact angle measurements. Overall, our findings challenge the standard assumption that MOFs must be prepared under highly dilute solvothermal conditions for optimal results, paving the way for their scalable and user-friendly synthesis in the laboratory.

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Metal–Organic Framework Seeding to Drive Phase Selection and Overcome Synthesis Limitations

Cited by 7 publications

References 22 publications

MOFganic Chemistry: Challenges and Opportunities for Metal-Organic Frameworks in Synthetic Organic Chemistry

MOFganic Chemistry: Challenges and Opportunities for Metal-Organic Frameworks in Synthetic Organic Chemistry

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

High-Concentration Self-Assembly of Zirconium- and Hafnium-Based Metal-Organic Materials

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