Contents
Cover
Title Page
Copyright
Preface
Reference
Contributors
Chapter 1: From Hofmann Complexes to Organic Coordination Networks
1.1 Introduction
1.2 Discovery of a Coordination Network
1.3 Organic Coordination Network: Organic Modification of the Hofmann Complex
1.4 M-Bipyridine Square Grids: Two-Way Link. Toward New Functions and Applications of Organic Coordination Networks
1.5 Single-Crystal-to-Single-Crystal Phenomena in Porous Coordination Networks
1.6 Expansion From Two- to Three-Way Link: Construction of TPT Coordination Networks
1.7 Biporous Coordination Networks
1.8 Concluding Remarks
References
Chapter 2: Insight into the Development of Metal-Organic Materials (MOMs): At Zeolite-like Metal-Organic Frameworks (ZMOFs)
2.1 Introduction
2.2 Metal-Organic Materials (MOMs)
2.3 Conclusion
References
Chapter 3: Topology and Interpenetration
3.1 Introduction
3.2 Nomenclature
3.3 Common 2D Nets
3.4 Common 3D Nets
3.5 Interpenetration
References
Chapter 4: Highly Connected Metal-Organic Frameworks
4.1 Introduction
4.2 Metal Cations as Highly Connected Nodes
4.3 Metal Clusters as Highly Connected Nodes
4.4 Framework Topologies
4.5 Conclusions
Acknowledgments
References
Chapter 5: Surface Pore Engineering of Porous Coordination Polymers
5.1 Introduction
5.2 Pore Surface with OMSs
5.3 Pore Surface with Functional Organic Sites (FOS)
5.4 Post-synthetic Pore Surface Modifications
5.5 Summary and Perspectives
Acknowledgment
References
Chapter 6: Rational Design of Non-centrosymmetric Metal-Organic Frameworks for Second-Order Nonlinear Optics
6.1 Introduction
6.2 Design Strategies for Non-Centrosymmetric Metal-Organic Frameworks
6.3 Non-Centrosymmetric Metal-Organic Frameworks for Second-Order Nonlinear Optical Applications
6.4 Conclusions and Outlook
Acknowledgments
References
Chapter 7: Selective Sorption of Gases and Vapors in Metal-Organic Frameworks
7.1 Introduction
7.2 Selective Gas Sorption by MOFs
7.3 Selective Vapor Sorption by MOFs
7.4 Potential Applications in Practical Separation Processes
7.5 Conclusions
Acknowledgments
List of abbreviations
Note Added in Proof
References
Chapter 8: Hydrogen and Methane Storage in Metal-Organic Frameworks
8.1 Introduction 1, 2
8.2 Hydrogen Storage
8.3 Methane Storage
8.4 Outlook
References
Chapter 9: Towards Mechanochemical Synthesis of Metal-Organic Frameworks: From Coordination Polymers and Lattice Inclusion Compounds to Porous Materials
9.1 Introduction
9.2 Advantages and Limitations of Mechanosynthesis
9.3 Methods for Mechanosynthesis of Coordination Bonds
9.4 Mechanochemical Reactivity Leading to Coordination Polymers
9.5 Construction of Coordination Polymers by Grinding
9.6 Related NonConventional Techniques
9.7 Conclusion
Acknowledgments
List of abbreviations
References
Chapter 10: Metal-Organic Frameworks with Photochemical Building Units
10.1 Introduction
10.2 [2 + 2] Photodimerization in the Solid State
10.3 [2 + 2] Photodimerizations Integrated into MOFs
10.4 Cyclobutanes as Organic Bridges of MOFs
10.5 Conclusion
References
Chapter 11: Molecular Modeling of Adsorption and Diffusion in Metal-Organic Frameworks
11.1 Models and Methods
11.2 Molecular Modeling of Adsorption in MOFs
11.3 Molecular Modeling of Diffusion in MOFs
11.4 Molecular Modeling of Hydrogen Storage in MOFs
11.5 Summary and Future Directions
Acknowledgments
References
Index
Copyright © 2010 by John Wiley & Sons, Inc. All rights reserved.
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Library of Congress Cataloging-in-Publication Data:
Metal-organic frameworks: design and application / edited by Leonard R. MacGillivray.
p. cm.
Includes index.
ISBN 978-0-470-19556-7 (cloth)
1. Supramolecular organometallic chemistry. 2. Organometallic polymers. 3. Porous materials. I. MacGillivray, Leonard R.
QD882.M48 2010
5470'.0504426-dc22
2009049259
Preface
The field of metal-organic frameworks, or MOFs, is undergoing accelerated and sustained growth. I personally became acquainted with MOFs, or more generally coordination polymers, as an undergraduate research student while at Saint Mary's University, Halifax, Nova Scotia, Canada, from 1991 to 1994. The process of mixing readily available metal precursors with organic linkers—many of which fell under the heading of being commercially available—to produce a wide array of extended frameworks clearly then, and now, captured the imagination of chemists and materials scientists worldwide.
From a fundamental standpoint, there is an important link between MOF chemistry and the field of inorganic chemistry. In many ways, MOF chemistry enables chemists to connect previously existing coordination complexes so as to make a conceptual link into the field of materials chemistry. This link has now evolved to afford applications ranging from catalysis to energy storage. Organic chemists are also able to contribute to the mix by crafting ligands with properties that one ultimately plans to express within the walls of MOFs. Solid-state chemists and X-ray crystallographers provide insights into the structures of MOFs so that the process of designing and synthesizing MOFs can be refined so as to ultimately control a targeted property and give rise to function.
My personal draw to MOFs was, in retrospect, also inspired by the field of supramolecular chemistry, particularly as it relates to the rational design of solids, or crystal engineering. The early 1990s witnessed supramolecular chemistry envelop the process of self-assembly, with a crystal being regarded as a supermolecule par excellence. [1] Metal–ligand bonding is reversible and, thus, fits within the realm of supramolecular chemistry. Self-assembly involves subunits of a larger superstructure being repeated in zero-dimensional (0D), 1D, 2D, or 3D space, with the solid state being a perfect resting place for intermolecular forces to dominate. Today, many of the boundaries between these areas have become increasingly more difficult to distinguish, which can be expected as more is being uncovered and as more emphasis is placed on properties and function.
It is, thus, with great pleasure that I am able to assemble a multi-author monograph that includes authoritative contributions from leading research laboratories in the field of MOF chemistry. My goal is to provide insights into where the field of MOFs began to take root and provide an account of the fundamentals that define where the field has come and is able to go. Indeed, MOFs provide chemists a means to think about how to utilize coordination space to mimic the chemistry of zeolites with an added degree of organic function. These possibilities have become apparent in key developments and important advances that are outlined in the chapters that follow.
Fujita (Chapter 1) and Eddaoudi (Chapter 2), for example, document the first reports of MOFs, or coordination networks, particularly those that exhibit catalysis, the emergence of heteroaromatic ligands, and how carboxylates provided an important entry to increasingly robust solids. Batten (Chapter 3) demonstrates a role of symmetry in defining and understanding the simple and complex frameworks that result from the solid-state assembly process that affords a MOF. Next, Schroder (Chapter 4) addresses the design and synthesis of extended frameworks of increasingly structural complexity in the form of highly connected MOFs based on lanthanide ions. Kitagawa (Chapter 5) then shows how the internal structures of coordination networks can be rationally modified and tailored with organic groups while Lin (Chapter 6) documents some of the first systematic applications of MOFs as they relate to the generation of nonlinear optic materials. A great challenge facing mankind is making efficient use of energy. MOFs have emerged as potentially useful platforms for facing this challenge in the form of gas storage, separation, and conversion. Thus, Kim (Chapter 7) and Zhou (Chapter 8) address how MOFs interact with small gas molecules (e.g., H2) and how these materials may be integrated into schemes for energy utilization. In a related topic, Friscic (Chapter 9) tackles the emerging issue of mechanochemical, or solvent-free, “green” preparation of MOFs while work by our group demonstrates how the walls of extended frameworks can be designed to serve as platforms for light-induced chemical reactions (Chapter 10). Finally, Snurr (Chapter 11) addresses how the field of computational chemistry can be used to understand, and ultimately, aide the design of MOFs, with targeted applications in separations, gas uptake, and materials characterization. Carefully chosen references serve to guide the reader through the extensive literature, which makes the field accessible to a wide and varied audience.
My initial interests in the chemistry of MOFs, and supramolecular chemistry and solid-state chemistry in general, stemmed from an experience as an undergraduate researcher. It is for this reason that I dedicate this monograph to the undergraduate research experience and to all of those that support undergraduate research.
Leonard R. MacGillivray
Iowa City, IA
March 2010
Reference
1. Dunitz, J. D. Pure Appl. Chem. 1991, 63, 177.
Contributors
Stuart R. Batten, School of Chemistry, Clayton Campus, Bldg. 19, Monash University, 3800 Australia
Neil R.Champness, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK
Hyungphil Chun, Department of Applied Chemistry, College of Science and Technology, Hanyang University, 1271 Sadong, Ansan 426-791, Republic of Korea
David J. Collins, Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; Department of Chemistry, Texas A&M University, College Station, TX 77843, USA
David Dubbeldam, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA
Saikat Dutta, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Mohamed Eddaoudi, Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE204, Tampa, FL 33620, USA
Jarrod F. Eubank, Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE204, Tampa, FL 33620, USA
Tomislav Friši, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
Houston Frost, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA
Makoto Fujita, Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan
Ivan G. Georgiev, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Sujit K. Ghosh, Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan; Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pune, India
Peter Hubberstey, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK
Hyunuk Kim, National Creative Research Initiative Center for Smart Supramolecules, Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang, 790-784, Republic of Korea
Kimoon Kim, National Creative Research Initiative Center for Smart Supramolecules, Department of Chemistry and Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang, 790-784, Republic of Korea
Susumu Kitagawa, Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615–851 Japan; Kitagawa Integrated Pore Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST), Shimogyoku, Kyoto 600-8815, Japan; Institute for Cell Materials Sciences (iCeMS), Kyoto University, Sokyo-ku, Kyoto, Japan
Wenbin Lin, Department of Chemistry, CB3290, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA
Xiang Lin, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK
Shengqian Ma, Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; Department of Chemistry, Texas A&M University, College Station, TX 77843, USA
Leonard R. MacGillivray, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Martin Schröder, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK
Randall Q. Snurr, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA
A. ˝zgr Yazaydin, Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road E136, Evanston, IL 60208, USA
Shuting Wu, Department of Chemistry, CB3290, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, USA
Hong-Cai Zhou, Department of Chemistry and Biochemistry, Miami University, Oxford, OH 45056, USA; Department of Chemistry, Texas A&M University, College Station, TX 77843, USA