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Title: In Situ, Time-Resolved, and Mechanistic Studies of Metal–Organic Framework Nucleation and Growth

Journal Article · · Chemical Reviews

The vast chemical and structural diversity of metal–organic frameworks (MOFs) opens up the exciting possibility of “crystal engineering” MOFs tailored for particular catalytic or separation applications. Yet the process of reaction discovery, optimization, and scale-up of MOF synthesis remains extremely challenging, presenting significant obstacles to the synthetic realization of many otherwise promising MOF structures. Recently, significant new insights into the fundamental processes governing MOF nucleation and growth, as well as the relationship between reaction parameters and synthetic outcome, have been derived using powerful in situ, time-resolved and/or mechanistic studies of MOF crystallization. This Review provides a summary and associated critical analysis of the results of these and other related “direct” studies of MOF nucleation and growth, with a particular emphasis on the recent advances in instrument technologies that have enabled such studies and on the major hypotheses, theories, and models that have been used to explain MOF formation. We conclude with a summary of the major insights that have been gained from the work summarized in this Review, outlining our own perspective on potential fruitful new directions for investigation.

Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0014059; DGE-1256259
OSTI ID:
1433911
Journal Information:
Chemical Reviews, Vol. 118, Issue 7; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 303 works
Citation information provided by
Web of Science

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Chiral Phosphoric Acids in Metal-Organic Frameworks with Enhanced Acidity and Tunable Catalytic Selectivity journal September 2019
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Structural Transformation in Metal-Organic Frameworks for Reversible Binding of Oxygen journal March 2019
Hypervalent silicon-based, anionic porous organic polymers with solid microsphere or hollow nanotube morphologies and exceptional capacity for selective adsorption of cationic dyes journal January 2019
Facet-dependent photocatalytic hydrogen production of metal–organic framework NH 2 -MIL-125(Ti) journal January 2019
Solvent Directed Synthesis of Molecular Cage and Metal Organic Framework of Copper(II) Paddlewheel Cluster journal October 2018
Molecular chains of coordinated dimolybdenum isonicotinate paddlewheel clusters journal January 2019
Coordination Assemblies of Zn(II) Coordination Polymers: Positional Isomeric Effect and Optical Properties journal December 2019
Single-crystal-to-single-crystal post-synthetic modifications of three-dimensional LOFs (Ln = Gd, Eu): a way to modulate their luminescence and thermometric properties journal January 2020
Metal−Organic Frameworks for High‐Energy Lithium Batteries with Enhanced Safety: Recent Progress and Future Perspectives journal April 2019
Syntheses, Crystal Structures, and Properties of New Coordination Polymers Incorporating 3,3-Dimethylcyclopropane-1,2-dicarboxylate and 4,4′-Bipyridine Ligands: Syntheses, Crystal Structures, and Properties of New Coordination Polymers Incorporating 3,3-Dimethylcyclopropane-1,2-dicarboxylate and 4,4′-Bipyridin journal September 2018
Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 syntheses journal August 2019
Highly Transparent, Flexible, and Mechanically Strong Nanopapers of Cellulose Nanofibers @Metal–Organic Frameworks journal February 2019
New Directions in Metal Phosphonate and Phosphinate Chemistry journal May 2019
Structural Transformation in Metal–Organic Frameworks for Reversible Binding of Oxygen journal March 2019
Probing the dynamics of Cu nanoparticle growth inside metal-organic frameworks upon electron beam irradiation journal September 2020
Insights into Functionalization of Metal-Organic Frameworks Using In Situ NMR Spectroscopy journal December 2018

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