Introduction to Reticular Chemistry

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.

• About the Companion Website xviiForeword xixAcknowledgment xxiIntroduction xxiiiAbbreviations xxviiPart I Metal-Organic Frameworks 11 Emergence of Metal-Organic Frameworks 31.1 Introduction 31.2 Early Examples of Coordination Solids 31.3 Werner Complexes 41.4 Hofmann Clathrates 61.5 Coordination Networks 81.6 Coordination Networks with Charged Linkers 151.7 Introduction of Secondary Building Units and Permanent Porosity 161.8 Extending MOF Chemistry to 3D Structures 171.9 Summary 23References 242 Determination and Design of Porosity 292.1 Introduction 292.2 Porosity in Crystalline Solids 292.3 Theory of Gas Adsorption 312.4 Porosity in Metal-Organic Frameworks 402.5 Summary 52References 523 Building Units of MOFs 573.1 Introduction 573.2 Organic Linkers 573.3 Secondary Building Units 713.4 Synthetic Routes to Crystalline MOFs 743.5 Activation of MOFs 773.6 Summary 79References 804 Binary Metal-Organic Frameworks 834.1 Introduction 834.2 MOFs Built from 3-, 4-, and 6-Connected SBUs 834.3 MOFs Built from 7-, 8-, 10-, and 12-Connected SBUs 974.4 MOFs Built from Infinite Rod SBUs 1124.5 Summary 114References 1145 Complexity and Heterogeneity in MOFs 1215.1 Introduction 1215.2 Complexity in Frameworks 1235.3 Heterogeneity in Frameworks 1355.4 Summary 141References 1416 Functionalization of MOFs 1456.1 Introduction 1456.2 In situ Functionalization 1466.3 Pre-Synthetic Functionalization 1496.4 Post-Synthetic Modification 1496.5 Analytical Methods 1716.6 Summary 172References 173Part II Covalent Organic Frameworks 1777 Historical Perspective on the Discovery of Covalent Organic Frameworks 1797.1 Introduction 1797.2 Lewis’ Concepts and the Covalent Bond 1807.3 Development of Synthetic Organic Chemistry 1827.4 Supramolecular Chemistry 1837.5 Dynamic Covalent Chemistry 1877.6 Covalent Organic Frameworks 1897.7 Summary 192References 1938 Linkages in Covalent Organic Frameworks 1978.1 Introduction 1978.2 B–O Bond Forming Reactions 1978.3 Linkages Based on Schiff-Base Reactions 2018.4 Imide Linkage 2138.5 Triazine Linkage 2168.6 Borazine Linkage 2178.7 Acrylonitrile Linkage 2188.8 Summary 220References 2219 Reticular Design of Covalent Organic Frameworks 2259.1 Introduction 2259.2 Linkers in COFs 2279.3 2D COFs 2279.4 3D COFs 2389.5 Summary 241References 24210 Functionalization of COFs 24510.1 Introduction 24510.2 In situ Modification 24510.3 Pre-Synthetic Modification 24710.4 Post-Synthetic Modification 25010.5 Summary 263References 26411 Nanoscopic and Macroscopic Structuring of Covalent Organic Frameworks 26711.1 Introduction 26711.2 Top–Down Approach 26811.3 Bottom–Up Approach 27111.4 Monolayer Formation of Boroxine and Imine COFs Under Ultrahigh Vacuum 28111.5 Summary 281References 282Part III Applications of Metal-Organic Frameworks 28512 The Applications of Reticular Framework Materials 287References 28813 The Basics of Gas Sorption and Separation in MOFs 29513.1 Gas Adsorption 29513.2 Gas Separation 29913.3 Stability of Porous Frameworks Under Application Conditions 30913.4 Summary 310References 31014 CO2 Capture and Sequestration 31314.1 Introduction 31314.2 In Situ Characterization 31514.3 MOFs for Post-combustion CO2 Capture 32114.4 MOFs for Pre-combustion CO2 Capture 32614.5 Regeneration and CO2 Release 32714.6 Important MOFs for CO2 Capture 32914.7 Summary 332References 33215 Hydrogen and Methane Storage in MOFs 33915.1 Introduction 33915.2 Hydrogen Storage in MOFs 34015.3 Methane Storage in MOFs 34915.4 Summary 359References 35916 Liquid- and Gas-Phase Separation in MOFs 36516.1 Introduction 36516.2 Separation of Hydrocarbons 36616.3 Separation in Liquids 38216.4 Summary 386References 38717 Water Sorption Applications of MOFs 39517.1 Introduction 39517.2 Hydrolytic Stability of MOFs 39517.3 Water Adsorption in MOFs 40417.4 Tuning the Adsorption Properties of MOFs by Introduction of Functional Groups 41117.5 Adsorption-Driven Heat Pumps 41217.6 Water Harvesting from Air 41517.7 Design of MOFs with TailoredWater Adsorption Properties 42017.8 Summary 422References 423Part IV Special Topics 42918 Topology 43118.1 Introduction 43118.2 Graphs, Symmetry, and Topology 43118.3 Nomenclature 43918.4 The Reticular Chemistry Structure Resource (RCSR) Database 44418.5 Important 3-Periodic Nets 44518.6 Important 2-Periodic Nets 44718.7 Important 0-Periodic Nets/Polyhedra 44918.8 Summary 451References 45119 Metal-Organic Polyhedra and Covalent Organic Polyhedra 45319.1 Introduction 45319.2 General Considerations for the Design of MOPs and COPs 45319.3 MOPs and COPs Based on the Tetrahedron 45419.4 MOPs and COPs Based on the Octahedron 45619.5 MOPs and COPs Based on Cubes and Heterocubes 45719.6 MOPs Based on the Cuboctahedron 45919.7 Summary 461References 46120 Zeolitic Imidazolate Frameworks 46320.1 Introduction 46320.2 Zeolitic Framework Structures 46520.2.1 Zeolite-Like Metal-Organic Frameworks (Z-MOFs) 46520.2.2 Zeolitic Imidazolate Frameworks (ZIFs) 46720.3 Synthesis of ZIFs 46820.4 Prominent ZIF Structures 46920.5 Design of ZIFs 47120.5.1 The Steric Index ;; as a Design Tool 47220.5.1.1 Principle I: Control over the Maximum Pore Opening 47320.5.1.2 Principle II: Control over the Maximum Cage Size 47320.5.1.3 Principle III: Control over the Structural Tunability 47420.5.2 Functionalization of ZIFs 47520.6 Summary 476References 47721 Dynamic Frameworks 48121.1 Introduction 48121.2 Flexibility in Synchronized Dynamics 48221.2.1 Synchronized Global Dynamics 48221.2.1.1 Breathing in MOFs Built from Rod SBUs 48321.2.1.2 Breathing in MOFs Built from Discrete SBUs 48421.2.1.3 Flexibility Through Distorted Organic Linkers 48721.2.2 Synchronized Local Dynamics 48721.3 Independent Dynamics in Frameworks 49021.3.1 Independent Local Dynamics 49021.3.2 Independent Global Dynamics 49221.4 Summary 494References 494Index 497