Introduction to Reticular Chemistry

A much-needed introduction to the chemistry and design principles behind important metal-organic frameworks and related porous materials Reticular chemistry has been applied to synthesize new classes of porous materials that are successfully used for myriad applications in areas such as gas separation, catalysis, energy, and electronics. Introduction to Reticular Chemistry gives an unique overview of the principles of the chemistry behind metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and zeolitic imidazolate frameworks (ZIFs). Written by one of the pioneers in the field, this book covers all important aspects of reticular chemistry, including design and synthesis, properties and characterization, as well as current and future applications. Designed to be an accessible resource, the book is written in an easy-to-understand style. It includes an extensive bibliography and offers figures and videos of crystal structures that are available as an electronic supplement. Introduction to Reticular Chemistry: -Describes the underlying principles and design elements for the synthesis of important metal-organic frameworks (MOFs) and related materials -Discusses both real-life and future applications in various fields, such as clean energy and water adsorption -Offers all graphic material on a companion website -Provides first-hand knowledge by Omar Yaghi, one of the pioneers in the field, and his team. Aimed at graduate students in chemistry, structural chemists, inorganic chemists, organic chemists, catalytic chemists, and others, Introduction to Reticular Chemistry is a groundbreaking book that explores the chemistry principles and applications of MOFs, COFs, and ZIFs.

Auteur
Omar M. Yaghi is the James and Neeltje Tretter Chair Professor of Chemistry at University of California, Berkeley, and a Senior Faculty Scientist at Lawrence Berkeley National Laboratory, USA.

Markus J. Kalmutzki is a principal scientist at Parr Instrument GmbH in Frankfurt, Germany. Before he was a DFG-postdoctoral fellow in the group of Omar M. Yaghi at the Universtity of California, Berkeley.

Christian S. Diercks is currently pursuing his Ph.D. in the group of Omar M. Yaghi at the University of California, Berkeley.

Contenu

About the Companion Website xvii

Foreword xix

Acknowledgment xxi

Introduction xxiii

Abbreviations xxvii

Part I Metal-Organic Frameworks 1

1 Emergence of Metal-Organic Frameworks 3

1.1 Introduction 3

1.2 Early Examples of Coordination Solids 3

1.3 Werner Complexes 4

1.4 Hofmann Clathrates 6

1.5 Coordination Networks 8

1.6 Coordination Networks with Charged Linkers 15

1.7 Introduction of Secondary Building Units and Permanent Porosity 16

1.8 Extending MOF Chemistry to 3D Structures 17

1.8.1 Targeted Synthesis of MOF-5 18

1.8.2 Structure of MOF-5 19

1.8.3 Stability of Framework Structures 20

1.8.4 Activation of MOF-5 20

1.8.5 Permanent Porosity of MOF-5 21

1.8.6 Architectural Stability of MOF-5 22

1.9 Summary 23

References 24

2 Determination and Design of Porosity 29

2.1 Introduction 29

2.2 Porosity in Crystalline Solids 29

2.3 Theory of Gas Adsorption 31

2.3.1 Terms and Definitions 31

2.3.2 Physisorption and Chemisorption 31

2.3.3 Gas Adsorption Isotherms 33

2.3.4 Models Describing Gas Adsorption in Porous Solids 35

2.3.4.1 Langmuir Model 37

2.3.4.2 BrunauerEmmettTeller (BET) Model 38

2.3.5 Gravimetric Versus Volumetric Uptake 40

2.4 Porosity in Metal-Organic Frameworks 40

2.4.1 Deliberate Design of Pore Metrics 40

2.4.2 Ultrahigh Surface Area 46

2.5 Summary 52

References 52

3 Building Units of MOFs 57

3.1 Introduction 57

3.2 Organic Linkers 57

3.2.1 Synthetic Methods for Linker Design 59

3.2.2 Linker Geometries 62

3.2.2.1 Two Points of Extension 62

3.2.2.2 Three Points of Extension 64

3.2.2.3 Four Points of Extension 64

3.2.2.4 Five Points of Extension 69

3.2.2.5 Six Points of Extension 69

3.2.2.6 Eight Points of Extension 69

3.3 Secondary Building Units 71

3.4 Synthetic Routes to Crystalline MOFs 74

3.4.1 Synthesis of MOFs from Divalent Metals 74

3.4.2 Synthesis of MOFs from Trivalent Metals 76

3.4.2.1 Trivalent Group 3 Elements 76

3.4.2.2 Trivalent Transition Metals 76

3.4.3 Synthesis of MOFs from Tetravalent Metals 77

3.5 Activation of MOFs 77

3.6 Summary 79

References 80

4 Binary Metal-Organic Frameworks 83

4.1 Introduction 83

4.2 MOFs Built from 3-, 4-, and 6-Connected SBUs 83

4.2.1 3-Connected (3-c) SBUs 83

4.2.2 4-Connected (4-c) SBUs 84

4.2.3 6-Connected (6-c) SBUs 90

4.3 MOFs Built from 7-, 8-, 10-, and 12-Connected SBUs 97

4.3.1 7-Connected (7-c) SBUs 97

4.3.2 8-Connected (8-c) SBUs 98

4.3.3 10-Connected (10-c) SBUs 103

4.3.4 12-Connected (12-c) SBUs 105

4.4 MOFs Built from Infinite Rod SBUs 112

4.5 Summary 114

References 114

5 Complexity and Heterogeneity in MOFs 121

5.1 Introduction 121

5.2 Complexity in Frameworks 123

5.2.1 Mixed-Metal MOFs 123

5.2.1.1 Linker De-symmetrization 123

5.2.1.2 Linkers with Chemically Distinct Binding Groups 123

5.2.2 Mixed-Linker MOFs 126

5.2.3 The TBU Approach 132

5.2.3.1 Linking TBUs Through Additional SBUs 133

5.2.3.2 Linking TBUs Through Organic Linkers 134

5.3 Heterogeneity in Frameworks 135

5.3.1 Multi-Linker MTV-MOFs 136

5.3.2 Multi-Metal MTV-MOFs 136

5.3.3 Disordered Vacancies 139

5.4 Summary 141

References 141 **6 Functionalization of MO...