A concise 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 myraid 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.
Table of Contents:
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
1.9 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
2.4 Porosity in Metal-Organic Frameworks 40
2.5 Summary 52
References 52
3 Building Units of MOFs 57
3.1 Introduction 57
3.2 Organic Linkers 57
3.3 Secondary Building Units 71
3.4 Synthetic Routes to Crystalline MOFs 74
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
4.3 MOFs Built from 7-, 8-, 10-, and 12-Connected SBUs 97
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
5.3 Heterogeneity in Frameworks 135
5.4 Summary 141
References 141
6 Functionalization of MOFs 145
6.1 Introduction 145
6.2 In situ Functionalization 146
6.3 Pre-Synthetic Functionalization 149
6.4 Post-Synthetic Modification 149
6.5 Analytical Methods 171
6.6 Summary 172
References 173
Part II Covalent Organic Frameworks 177
7 Historical Perspective on the Discovery of Covalent Organic Frameworks 179
7.1 Introduction 179
7.2 Lewis’ Concepts and the Covalent Bond 180
7.3 Development of Synthetic Organic Chemistry 182
7.4 Supramolecular Chemistry 183
7.5 Dynamic Covalent Chemistry 187
7.6 Covalent Organic Frameworks 189
7.7 Summary 192
References 193
8 Linkages in Covalent Organic Frameworks 197
8.1 Introduction 197
8.2 B–O Bond Forming Reactions 197
8.3 Linkages Based on Schiff-Base Reactions 201
8.4 Imide Linkage 213
8.5 Triazine Linkage 216
8.6 Borazine Linkage 217
8.7 Acrylonitrile Linkage 218
8.8 Summary 220
References 221
9 Reticular Design of Covalent Organic Frameworks 225
9.1 Introduction 225
9.2 Linkers in COFs 227
9.3 2D COFs 227
9.4 3D COFs 238
9.5 Summary 241
References 242
10 Functionalization of COFs 245
10.1 Introduction 245
10.2 In situ Modification 245
10.3 Pre-Synthetic Modification 247
10.4 Post-Synthetic Modification 250
10.5 Summary 263
References 264
11 Nanoscopic and Macroscopic Structuring of Covalent Organic Frameworks 267
11.1 Introduction 267
11.2 Top–Down Approach 268
11.3 Bottom–Up Approach 271
11.4 Monolayer Formation of Boroxine and Imine COFs Under Ultrahigh Vacuum 281
11.5 Summary 281
References 282
Part III Applications of Metal-Organic Frameworks 285
12 The Applications of Reticular Framework Materials 287
References 288
13 The Basics of Gas Sorption and Separation in MOFs 295
13.1 Gas Adsorption 295
13.2 Gas Separation 299
13.3 Stability of Porous Frameworks Under Application Conditions 309
13.4 Summary 310
References 310
14 CO2 Capture and Sequestration 313
14.1 Introduction 313
14.2 In Situ Characterization 315
14.3 MOFs for Post-combustion CO2 Capture 321
14.4 MOFs for Pre-combustion CO2 Capture 326
14.5 Regeneration and CO2 Release 327
14.6 Important MOFs for CO2 Capture 329
14.7 Summary 332
References 332
15 Hydrogen and Methane Storage in MOFs 339
15.1 Introduction 339
15.2 Hydrogen Storage in MOFs 340
15.3 Methane Storage in MOFs 349
15.4 Summary 359
References 359
16 Liquid- and Gas-Phase Separation in MOFs 365
16.1 Introduction 365
16.2 Separation of Hydrocarbons 366
16.3 Separation in Liquids 382
16.4 Summary 386
References 387
17 Water Sorption Applications of MOFs 395
17.1 Introduction 395
17.2 Hydrolytic Stability of MOFs 395
17.3 Water Adsorption in MOFs 404
17.4 Tuning the Adsorption Properties of MOFs by Introduction of Functional Groups 411
17.5 Adsorption-Driven Heat Pumps 412
17.6 Water Harvesting from Air 415
17.7 Design of MOFs with TailoredWater Adsorption Properties 420
17.8 Summary 422
References 423
Part IV Special Topics 429
18 Topology 431
18.1 Introduction 431
18.2 Graphs, Symmetry, and Topology 431
18.3 Nomenclature 439
18.4 The Reticular Chemistry Structure Resource (RCSR) Database 444
18.5 Important 3-Periodic Nets 445
18.6 Important 2-Periodic Nets 447
18.7 Important 0-Periodic Nets/Polyhedra 449
18.8 Summary 451
References 451
19 Metal-Organic Polyhedra and Covalent Organic Polyhedra 453
19.1 Introduction 453
19.2 General Considerations for the Design of MOPs and COPs 453
19.3 MOPs and COPs Based on the Tetrahedron 454
19.4 MOPs and COPs Based on the Octahedron 456
19.5 MOPs and COPs Based on Cubes and Heterocubes 457
19.6 MOPs Based on the Cuboctahedron 459
19.7 Summary 461
References 461
20 Zeolitic Imidazolate Frameworks 463
20.1 Introduction 463
20.2 Zeolitic Framework Structures 465
20.2.1 Zeolite-Like Metal-Organic Frameworks (Z-MOFs) 465
20.2.2 Zeolitic Imidazolate Frameworks (ZIFs) 467
20.3 Synthesis of ZIFs 468
20.4 Prominent ZIF Structures 469
20.5 Design of ZIFs 471
20.5.1 The Steric Index ;; as a Design Tool 472
20.5.1.1 Principle I: Control over the Maximum Pore Opening 473
20.5.1.2 Principle II: Control over the Maximum Cage Size 473
20.5.1.3 Principle III: Control over the Structural Tunability 474
20.5.2 Functionalization of ZIFs 475
20.6 Summary 476
References 477
21 Dynamic Frameworks 481
21.1 Introduction 481
21.2 Flexibility in Synchronized Dynamics 482
21.2.1 Synchronized Global Dynamics 482
21.2.1.1 Breathing in MOFs Built from Rod SBUs 483
21.2.1.2 Breathing in MOFs Built from Discrete SBUs 484
21.2.1.3 Flexibility Through Distorted Organic Linkers 487
21.2.2 Synchronized Local Dynamics 487
21.3 Independent Dynamics in Frameworks 490
21.3.1 Independent Local Dynamics 490
21.3.2 Independent Global Dynamics 492
21.4 Summary 494
References 494
Index 497
About the Author :
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.
