Modulated Self-assembly of Metal-organic Frameworks

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 14

PMID 34122913

Citations 41

Authors

Ross S Forgan

Affiliations

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Abstract

Exercising fine control over the synthesis of metal-organic frameworks (MOFs) is key to ensuring reproducibility of physical properties such as crystallinity, particle size, morphology, porosity, defectivity, and surface chemistry. The principle of modulated self-assembly - incorporation of modulator molecules into synthetic mixtures - has emerged as the primary means to this end. This perspective article will detail the development of modulated synthesis, focusing primarily on coordination modulation, from a technique initially intended to cap the growth of MOF crystals to one that is now used regularly to enhance crystallinity, control particle size, induce defectivity and select specific phases. The various mechanistic driving forces will be discussed, as well as the influence of modulation on physical properties and how this can facilitate potential applications. Modulation is also increasingly being used to exert kinetic control over self-assembly; examples of phase selection and the development of new protocols to induce this will be provided. Finally, the application of modulated self-assembly to alternative materials will be discussed, and future perspectives on the area given.

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References

Trickett C, Gagnon K, Lee S, Gandara F, Burgi H, Yaghi O . Definitive molecular level characterization of defects in UiO-66 crystals. Angew Chem Int Ed Engl. 2015; 54(38):11162-7. DOI: 10.1002/anie.201505461. View

Morris W, Wang S, Cho D, Auyeung E, Li P, Farha O . Role of Modulators in Controlling the Colloidal Stability and Polydispersity of the UiO-66 Metal-Organic Framework. ACS Appl Mater Interfaces. 2017; 9(39):33413-33418. DOI: 10.1021/acsami.7b01040. View

Furukawa H, Gandara F, Zhang Y, Jiang J, Queen W, Hudson M . Water adsorption in porous metal-organic frameworks and related materials. J Am Chem Soc. 2014; 136(11):4369-81. DOI: 10.1021/ja500330a. View

Griffin S, Briuglia M, Ter Horst J, Forgan R . Assessing Crystallisation Kinetics of Zr Metal-Organic Frameworks through Turbidity Measurements to Inform Rapid Microwave-Assisted Synthesis. Chemistry. 2020; 26(30):6910-6918. PMC: 7318326. DOI: 10.1002/chem.202000993. View

Park J, Wang Z, Sun L, Chen Y, Zhou H . Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly. J Am Chem Soc. 2012; 134(49):20110-6. DOI: 10.1021/ja3085884. View

Calik M, Sick T, Dogru M, Doblinger M, Datz S, Budde H . From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks--A Modulation Approach. J Am Chem Soc. 2015; 138(4):1234-9. PMC: 4742964. DOI: 10.1021/jacs.5b10708. View

Abanades Lazaro I, Haddad S, Sacca S, Orellana-Tavra C, Fairen-Jimenez D, Forgan R . Selective Surface PEGylation of UiO-66 Nanoparticles for Enhanced Stability, Cell Uptake, and pH-Responsive Drug Delivery. Chem. 2017; 2(4):561-578. PMC: 5421152. DOI: 10.1016/j.chempr.2017.02.005. View

Guo H, Zhu Y, Qiu S, Lercher J, Zhang H . Coordination modulation induced synthesis of nanoscale Eu(1-x)Tb(x)-metal-organic frameworks for luminescent thin films. Adv Mater. 2010; 22(37):4190-2. DOI: 10.1002/adma.201000844. View

Marshall R, Griffin S, Wilson C, Forgan R . Single-Crystal to Single-Crystal Mechanical Contraction of Metal-Organic Frameworks through Stereoselective Postsynthetic Bromination. J Am Chem Soc. 2015; 137(30):9527-30. DOI: 10.1021/jacs.5b05434. View

10.

Rijnaarts T, Mejia-Ariza R, Egberink R, van Roosmalen W, Huskens J . Metal-Organic Frameworks (MOFs) as Multivalent Materials: Size Control and Surface Functionalization by Monovalent Capping Ligands. Chemistry. 2015; 21(29):10296-301. DOI: 10.1002/chem.201501974. View

11.

Cliffe M, Wan W, Zou X, Chater P, Kleppe A, Tucker M . Correlated defect nanoregions in a metal-organic framework. Nat Commun. 2014; 5:4176. PMC: 4730551. DOI: 10.1038/ncomms5176. View

12.

Canossa S, Gonzalez-Nelson A, Shupletsov L, Del Carmen Martin M, van der Veen M . Overcoming Crystallinity Limitations of Aluminium Metal-Organic Frameworks by Oxalic Acid Modulated Synthesis. Chemistry. 2020; 26(16):3564-3570. PMC: 7154786. DOI: 10.1002/chem.201904798. View

13.

Marshall R, Griffin S, Wilson C, Forgan R . Stereoselective Halogenation of Integral Unsaturated C-C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs. Chemistry. 2016; 22(14):4870-7. PMC: 5067641. DOI: 10.1002/chem.201505185. View

14.

Bon V, Senkovskyy V, Senkovska I, Kaskel S . Zr(IV) and Hf(IV) based metal-organic frameworks with reo-topology. Chem Commun (Camb). 2012; 48(67):8407-9. DOI: 10.1039/c2cc34246d. View

15.

Ji P, Manna K, Lin Z, Feng X, Urban A, Song Y . Single-Site Cobalt Catalysts at New Zr(μ-O)(μ-OH)(μ-OH) Metal-Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides. J Am Chem Soc. 2017; 139(20):7004-7011. DOI: 10.1021/jacs.7b02394. View

16.

Devic T, Serre C . High valence 3p and transition metal based MOFs. Chem Soc Rev. 2014; 43(16):6097-115. DOI: 10.1039/c4cs00081a. View

17.

Cheetham A, Bennett T, Coudert F, Goodwin A . Defects and disorder in metal organic frameworks. Dalton Trans. 2016; 45(10):4113-26. DOI: 10.1039/c5dt04392a. View

18.

Hermes S, Witte T, Hikov T, Zacher D, Bahnmuller S, Langstein G . Trapping metal-organic framework nanocrystals: an in-situ time-resolved light scattering study on the crystal growth of MOF-5 in solution. J Am Chem Soc. 2007; 129(17):5324-5. DOI: 10.1021/ja068835i. View

19.

Wu H, Chua Y, Krungleviciute V, Tyagi M, Chen P, Yildirim T . Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption. J Am Chem Soc. 2013; 135(28):10525-32. DOI: 10.1021/ja404514r. View

20.

Gutov O, Gonzalez Hevia M, Escudero-Adan E, Shafir A . Metal-Organic Framework (MOF) Defects under Control: Insights into the Missing Linker Sites and Their Implication in the Reactivity of Zirconium-Based Frameworks. Inorg Chem. 2015; 54(17):8396-400. DOI: 10.1021/acs.inorgchem.5b01053. View