Ionothermal Synthesis of Metal‐Organic Frameworks Using Low‐Melting Metal Salt Precursors**

Azbell, Tyler J.; Pitt, Tristan; Bollmeyer, Melissa M.; Cong, Christina; Lancaster, Kyle M.; Milner, Phillip J.

doi:10.1002/anie.202218252

Cited by 12 publications

(17 citation statements)

References 74 publications

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“…139 Our group has shown that ionothermal synthesis using lowmelting metal salt precursors provides access to a wide range of acid-stable MOFs by simply combining metal salts and organic linkers together at high temperatures. 140 Intriguingly, frameworks produced using this method possess crystallinity and porosity comparable to those synthesized under traditional dilute solvothermal conditions.…”

Section: Robustness Of Mofs For Organic Synthesismentioning

confidence: 88%

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: 88%

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

Ahmad

Keasler

Stacy

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…For example, ionothermal synthesis enables the preparation of porous materials without the need for organic solvents . Our group has shown that ionothermal synthesis using low-melting metal salt precursors provides access to a wide range of acid-stable MOFs by simply combining metal salts and organic linkers together at high temperatures . Intriguingly, frameworks produced using this method possess crystallinity and porosity comparable to those of frameworks synthesized under traditional dilute solvothermal conditions.…”

Section: User-friendly Mof Synthesismentioning

confidence: 99%

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

et al. 2023

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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 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 in drug synthesis. This Perspective aims to bring together the organic and MOF communities to develop new heterogeneous platforms capable of achieving synthetic transformations that cannot be replicated by homogeneous systems.

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“…47 Encouraged by this finding, we sought to prepare azolate and salicylate MOFs�materials that are especially promising for catalysis but are limited by dilute (<0.01 M) synthesis conditions and long (>7 days) reaction times�without solvent, utilizing low-melting molten metal (hydrate) salts as ionothermal media (Figure 5). 48 Starting with azolate MOFs, we identified the open-metal site M 2 Cl 2 (btdd) (M = V, Mn, Fe, Co, Ni, Cu) family of MOFs as promising candidates for ionothermal synthesis. 8 Indeed, combining the corresponding metal chloride hydrate salts with the H 2 btdd linker at temperatures above the melting point of the salt (160 °C), yields Co 2 Cl 2 (btdd) and Ni 2 Cl 2 (btdd) after 16 h. Notably, the temperatures at which these reactions are performed is below the melting or decomposition points of the corresponding linkers.…”

Section: Ionothermal Synthesismentioning

confidence: 99%

“…Starting with azolate MOFs, we identified the open-metal site M 2 Cl 2 (btdd) (M = V, Mn, Fe, Co, Ni, Cu) family of MOFs as promising candidates for ionothermal synthesis . Indeed, combining the corresponding metal chloride hydrate salts with the H 2 btdd linker at temperatures above the melting point of the salt (160 °C), yields Co 2 Cl 2 (btdd) and Ni 2 Cl 2 (btdd) after 16 h. Notably, the temperatures at which these reactions are performed is below the melting or decomposition points of the corresponding linkers . These samples can be purified from soluble impurities via Soxhlet extraction.…”

Section: Ionothermal Synthesismentioning

confidence: 99%

Simplifying the Synthesis of Metal–Organic Frameworks

Azbell,

Pitt,

Jerozal

et al. 2023

Acc. Mater. Res.

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Conspectus Metal–organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes that have attracted widespread interest due to their permanent porosity and highly modular structures. However, the large volumes of organic solvents and additives, long reaction times, and specialized equipment typically required to synthesize MOFs hinder their widespread adoption in both academia and industry. Recently, our lab has developed several user-friendly methods for the gram-scale (1–100 g) preparation of MOFs. Herein, we summarize our progress in the development of high-concentration solvothermal, mechanochemical, and ionothermal syntheses of MOFs, as well as in minimizing the amount of modulators required to prepare highly crystalline Zr-MOFs. To begin, we detail our work elucidating key features of acid modulation in Zr-MOFs to improve current dilute solvothermal syntheses. Choosing an optimal modulator maximizes the crystallinity and porosity of Zr-MOFs while minimizing the quantity of modulator needed and reducing the waste associated with MOF synthesis. By evaluating a range of modulators, we identify the pK a, size, and structural similarity of the modulator to the linker as controlling factors in modulating ability. In the following section, we describe two high-concentration solvothermal methods for the synthesis of Zr-MOFs and demonstrate their generality among a range of frameworks. We also target the M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd; dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) family of MOFs for high-concentration synthesis and introduce a two-step preparation of several variants that proceeds through a novel kinetic phase. The high-concentration methods we discuss produce MOFs on a multigram scale with comparable properties to those prepared under traditional dilute solvothermal conditions. Next, to further curtail solvent waste and accelerate reaction times, we discuss the mechanochemical preparation of M2(dobdc) MOFs utilizing liquid amine additives in a planetary ball mill, which we also apply to the synthesis of two related salicylate frameworks. These samples exhibit porosities comparable to those of traditional dilute solvothermal samples but can be synthesized in just minutes, as opposed to days, and require under 1 mL of liquid additive to prepare ∼0.5 g of material. In the following section, we discuss our efforts to avoid specialized equipment and eliminate solvent use entirely by employing ionothermal conditions to prepare a variety of azolate- and salicylate-based MOFs. Simply combining metal chloride (hydrate) salts with organic linkers at temperatures above the melting points of the salts affords high-quality framework materials. Further, ionothermal conditions enable the syntheses of two new Fe(III) M2(dobdc) derivatives that cannot be synthesized under normal solvothermal conditions. Last, as a demonstrative example, we discuss our efforts to synthesize 100 g of high-quality Mg2(dobdc) in a single batch using a high-concentrat...

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Ionothermal Synthesis of Metal‐Organic Frameworks Using Low‐Melting Metal Salt Precursors**

Cited by 12 publications

References 74 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

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

Simplifying the Synthesis of Metal–Organic Frameworks

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