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

Overview

Journal Chem Mater

Date 2024 Jan 15

PMID 38222037

Authors

Bayu I Z Ahmad

Kaitlyn T Keasler

Emily E Stacy

Sijing Meng

Thomas J Hicks

Phillip J Milner

Affiliations

Soon will be listed here.

Abstract

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 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 cannot be replicated by homogeneous systems.

Citing Articles

Organic and Metal-Organic Polymer-Based Catalysts-Enfant Terrible Companions or Good Assistants?.

Kralik M, Koos P, Markovic M, Lopatka P Molecules. 2024; 29(19).

PMID: 39407552 PMC: 11477782. DOI: 10.3390/molecules29194623.

Gas Delivery Relevant to Human Health using Porous Materials.

Mandel R, Lotlikar P, Keasler K, Chen E, Wilson J, Milner P Chemistry. 2024; 30(51):e202402163.

PMID: 38949770 PMC: 11443428. DOI: 10.1002/chem.202402163.

Cobalt(III) Halide Metal-Organic Frameworks Drive Catalytic Halogen Exchange.

Azbell T, Milner P J Am Chem Soc. 2024; .

PMID: 38607314 PMC: 11470105. DOI: 10.1021/jacs.3c13872.

Simplifying the Synthesis of Metal-Organic Frameworks.

Azbell T, Pitt T, Jerozal R, Mandel R, Milner P Acc Mater Res. 2024; 4(10):867-878.

PMID: 38226178 PMC: 10788152. DOI: 10.1021/accountsmr.3c00121.

References

Wang Z, Li Z, Ng M, Milner P . Rapid mechanochemical synthesis of metal-organic frameworks using exogenous organic base. Dalton Trans. 2020; 49(45):16238-16244. DOI: 10.1039/d0dt01240h. View

Kerru N, Gummidi L, Maddila S, Gangu K, Jonnalagadda S . A Review on Recent Advances in Nitrogen-Containing Molecules and Their Biological Applications. Molecules. 2020; 25(8). PMC: 7221918. DOI: 10.3390/molecules25081909. View

Wei Y, Zhang M, Zou R, Xu Q . Metal-Organic Framework-Based Catalysts with Single Metal Sites. Chem Rev. 2020; 120(21):12089-12174. DOI: 10.1021/acs.chemrev.9b00757. View

Zhang Y, Diver S . A Macrocyclic Ruthenium Carbene for Size-Selective Alkene Metathesis. J Am Chem Soc. 2020; 142(7):3371-3374. DOI: 10.1021/jacs.0c00081. View

Zhang J, An B, Li Z, Cao Y, Dai Y, Wang W . Neighboring Zn-Zr Sites in a Metal-Organic Framework for CO Hydrogenation. J Am Chem Soc. 2021; 143(23):8829-8837. DOI: 10.1021/jacs.1c03283. View

Li Y, Wen G, Li J, Li Q, Zhang H, Tao B . Synthesis and shaping of metal-organic frameworks: a review. Chem Commun (Camb). 2022; 58(82):11488-11506. DOI: 10.1039/d2cc04190a. View

Khan M, Rahman A, Matussin S . Recent Progress of Metal-Organic Frameworks and Metal-Organic Frameworks-Based Heterostructures as Photocatalysts. Nanomaterials (Basel). 2022; 12(16). PMC: 9413115. DOI: 10.3390/nano12162820. View

Forgan R . Modulated self-assembly of metal-organic frameworks. Chem Sci. 2021; 11(18):4546-4562. PMC: 8159241. DOI: 10.1039/d0sc01356k. View

Wang D, Zhang B, He C, Wu P, Duan C . A new chiral N-heterocyclic carbene silver(I) cylinder: synthesis, crystal structure and catalytic properties. Chem Commun (Camb). 2010; 46(26):4728-30. DOI: 10.1039/c000793e. View

10.

Dhakshinamoorthy A, Garcia H . Metal-organic frameworks as solid catalysts for the synthesis of nitrogen-containing heterocycles. Chem Soc Rev. 2014; 43(16):5750-65. DOI: 10.1039/c3cs60442j. View

11.

Farha O, Eryazici I, Jeong N, Hauser B, Wilmer C, Sarjeant A . Metal-organic framework materials with ultrahigh surface areas: is the sky the limit?. J Am Chem Soc. 2012; 134(36):15016-21. DOI: 10.1021/ja3055639. View

12.

Hofer C, Grass R, Schneider E, Hendriks L, Herzog A, Zeltner M . Water dispersible surface-functionalized platinum/carbon nanorattles for size-selective catalysis. Chem Sci. 2018; 9(2):362-367. PMC: 5868313. DOI: 10.1039/c7sc03785f. View

13.

Yuan N, Pascanu V, Huang Z, Valiente A, Heidenreich N, Leubner S . Probing the Evolution of Palladium Species in Pd@MOF Catalysts during the Heck Coupling Reaction: An Operando X-ray Absorption Spectroscopy Study. J Am Chem Soc. 2018; 140(26):8206-8217. DOI: 10.1021/jacs.8b03505. View

14.

Howard J, Cao Q, Browne D . Mechanochemistry as an emerging tool for molecular synthesis: what can it offer?. Chem Sci. 2018; 9(12):3080-3094. PMC: 5933221. DOI: 10.1039/c7sc05371a. View

15.

Ding M, Cai X, Jiang H . Improving MOF stability: approaches and applications. Chem Sci. 2020; 10(44):10209-10230. PMC: 7069376. DOI: 10.1039/c9sc03916c. View

16.

Chen E, Mandel R, Milner P . Evaluating Solvothermal and Mechanochemical Routes towards the Metal-Organic Framework Mg(-dobdc). CrystEngComm. 2023; 24(41):7292-7297. PMC: 9910849. DOI: 10.1039/d2ce00739h. View

17.

Wang C, Gao W, Powers D . Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru-Based Metal-Organic Framework. J Am Chem Soc. 2019; 141(49):19203-19207. DOI: 10.1021/jacs.9b09620. View

18.

Kumawat L, Wynne C, Cappello E, Fisher P, Brennan L, Strofaldi A . Squaramide-Based Self-Associating Amphiphiles for Anion Recognition. Chempluschem. 2021; 86(8):1058-1068. PMC: 8456826. DOI: 10.1002/cplu.202100275. View

19.

Zhou T, Auer B, Lee S, Telfer S . Catalysts Confined in Programmed Framework Pores Enable New Transformations and Tune Reaction Efficiency and Selectivity. J Am Chem Soc. 2019; 141(4):1577-1582. DOI: 10.1021/jacs.8b11221. View

20.

Ding R, Liu Q, Zheng L . Piezoelectric Metal-Organic Frameworks Mediated Mechanoredox Borylation and Arylation Reactions by Ball Milling. Chemistry. 2023; 29(20):e202203792. DOI: 10.1002/chem.202203792. View