Metal-Organic Frameworks with Heterogeneous Structures

1 Cover

2 Title Page

3 Copyright

4 List of Illustrations

5 List of Tables

6 List of Schemes

7 Preface

8 Abbreviations

9 1 Introduction: A Brief Introduction About Metal-Organic Frameworks 1.1 Metal-Organic Frameworks 1.2 Conclusion References

10 2 Metal-Organic Frameworks Complexity 2.1 Perspectives on Complexity in MOFs 2.2 Conclusion References

11 3 Complexity Based on Ligand—Part 1 3.1 Mixed Ligand 3.2 Conclusion References

12 4 Complexity Based on Ligand—Part 2 4.1 Polytopic Linkers 4.2 Multi-Heterotopic Ligands 4.3 Conclusion References

13 5 Complexity Based on Metal Node 5.1 Mixed Metal 5.2 Multiple SBUs 5.3 Conclusion References

14 6 Complexity Based on Chiral Framework—Part 1 6.1 Inherent Chirality 6.2 Direct Chirality 6.3 Conclusion References

15 7 Complexity Based on Chiral Framework—Part 2 7.1 Chiral-Template Synthesis 7.2 Post-Synthesis 7.3 Conclusion References

16 8 Complexity Based on Structural Defects 8.1 Inherent Defect 8.2 Designed Defect 8.3 Conclusion References

17 9 Complexity Based on Heterogeneous Pores 9.1 Heterogeneous Pores 9.2 Conclusion References

18 10 Complexity Based on Mixed MOFs 10.1 Complex Mixed MOFs 10.2 Conclusion References

19 Index

20 Also of Interest

21 End User License Agreement

1 Chapter 3Table 3.1 Examples of mixed ligands metal-organic frameworks.Table 3.2 Determination of catalytic conditions for Biginelli reaction.

2 Chapter 5Table 5.1 Optimization of the carboxylation of phenylacetylene a.Table 5.2 Carboxylation of terminal alkynes with CO 2 a.Table 5.3 Crystallographic data and refinement parameters of the considered MOF.Table 5.4 Various applications of mixed-metal MOFs.

3 Chapter 6Table 6.1 Diethylzinc additions to aromatic aldehydes.Table 6.2 Alkynylzinc additions to aromatic aldehydes (similar conditions with T...

4 Chapter 7Table 7.1 Asymmetric dihydroxylation of aryl olefins. aTable 7.2 Aldol reactions catalyzed by Zn-MOF1. aTable 7.3 Aldol reactions by using Zn-MOF1 and Zn-MOF2.Table 7.4 Control reactions for asymmetric epoxidation of styrene. aTable 7.5 Asymmetric epoxidation of several olefins and methanolysis of styrene ...

5 Chapter 8Table 8.1 Some of the published papers about defects in metal-organic frameworks...Table 8.2 Some of defective MOF-based materials.

6 Chapter 10Table 10.1 Carbon dioxide cycloaddition with various epoxides by using CZ-BDO. a

1 Chapter 1 Figure 1.1 Simple description of 3D MOF chemistry [1]. Figure 1.2 Some examples of metal nodes, organic linkers, and MOFs (definition o... Figure 1.2 (Continued) Some examples of metal nodes, organic linkers, and MOFs (... Figure 1.2 (Continued) Some examples of metal nodes, organic linkers, and MOFs (... Figure 1.3 Some examples of MOFs synthesis methods.

2 Chapter 2 Figure 2.1 Simple language to understand concept of complexity [45]. Figure 2.2 Overview of this book based on the effective factors in the construct... Figure 2.3 Classification of complexity key factors in MOFs (further details in ... Figure 2.4 A cost-effective mixed-metal mixed-ligand MOF, which exhibits highly ... Scheme 2.1 The conversion of an achiral MOF to a chiral MOF by using an achiral ... Figure 2.5 Defective linker concept for defect-engineered MOFs [44].

3 Chapter 3Figure 3.1 A photocatalyst MOF with three different ditopic linkers [9].Figure 3.2 Structural analyses of a MOF-based photocatalyst with three different...Scheme 3.1 Structure of the used ligands.Figure 3.3 (a) Copper-phosphonate CBU polyhedral. Octahedral Cu1 and square pyra...Figure 3.4 Schematic representations of the happened processes in MOF with incre...Figure 3.4 (Continued) Schematic representations of the happened processes in MO...Figure 3.5 Schematic representations of construction mechanism. (a) Formed micro...Figure 3.5 (Continued) Schematic representations of construction mechanism.(a) F...Figure 3.6 One kind of mixed-valence Ru II/IIIMOF with mixed-linker [23].Figure 3.7 Olefin hydrogenation mechanism [23].Figure 3.8 Zeolite-like MOFs based on mixed linkers [43].Figure 3.9 A mixed-ligand MOF with two ligands BTC (benzene-1,3,5-tricarboxylate...Figure 3.10 Stepwise preparation of {[Cu 4(CDC) 4(4,4′-bipy)(H 2O) 2] 3} n·xS. Copper:...Figure 3.11 ADES-1: (a) coordination environment around Zn(II); (b) and (c) [Zn 2...Figure 3.12 ADES-2: (a) coordination environment around Cd(II); (b) and (c) [Cd 2...Scheme 3.2 Structures of the used organic dyes.Scheme 3.3 Biginelli reaction by using ADES-1.Figure 3.13 Direct synthesis of mixed-ligands MOF film, RuB-RuTB-UiO-67/TiO 2/FTO...

4 Chapter 4Figure 4.1 Some of the tritopic linkers.Figure 4.2 The symmetry in organic linker. Tetratopic linkers with (a) symmetry ...Figure 4.3 Some of the tetratopic linkers.Figure 4.4 A mixed-ligand MOF with tetratopic organic linkers [10].Figure 4.5 Some of the multi-topic linkers.Figure 4.6 A kind of MOF with multi-hetero topic organic linker [4].Figure 4.7 (a) Cu(II) Coordination environment. Symmetric nodes: (i) y, 1 - x, 1...

5 Chapter 5Figure 5.1 Two synthesis strategies to create MM′-MOFs.Figure 5.2 Two synthetic methods to create 2D gird MM′-MOFs [36].Figure 5.3 The incorporated BPDC, RuDCBPY, and PtDCBPY into Zr-MOF (UiO-67) thro...Figure 5.4 (a) Powder x-ray diffraction patterns, (b) IR spectra, and (c) TGA an...Figure 5.5 (a–c) SEM and (d–j) HAADF-STEM images of the considered samples (top)...Figure 5.6 The formation of coordination polymers from the corresponding metals ...Figure 5.7 The epitaxial growth of the trimetallic and bimetallic hetero-(Ln)-MO...Figure 5.8 Transmetalation in porph@MOM-10 (a) and MSO-MOF (b). [Panel (b): meta...Figure 5.9 (a) 3D structure of [Gd 3Cu 12I 12(IN) 9(DMF) 4] n.nDMF. (structure I) (b) ...Figure 5.10 The solid-state luminescent properties of MOFs with diverse SBUs [58...Figure 5.11 (a and b) MOF 1 structure showing Co 3SBU supported by Co1 and Co2 v...

6 Chapter 6Figure 6.1 (a) Two types of chiral tetrahedral SBUs. (b) A perspective view of m...Figure 6.2 (a) Schematic representation of a chiral MOF catalyst by PSM. (b) The...Figure 6.3 Crystal structure of chiral MOF-1a. (a) Paddle-wheels clusters based ...Figure 6.3 (Continued) Crystal structure of chiral MOF-1a. (a) Paddle-wheels clu...Scheme 6.1 Synthesis conditions to produce chiral metal-camphorate coordination ...Scheme 6.2 Coordination modes of D-Cam and D-HCam in polymeric structures 1–5.Figure 6.4 (a and b) Views of connectivity around metallic centers in structure ...Figure 6.5 Total synthesis of CMOF with chiral axial ligand [59].Figure 6.6 Different cavity sizes in CMOFs [58].Figure 6.7 Stick/polyhedra models of CMOF-1-5 with the presence of interpenetrat...

7 Chapter 7Figure 7.1 An example of the chiral templating effect origin [1].Figure 7.2 Synthesis method of Ni-PYI1, guest exchange, and the considered asymm...Figure 7.3 Examples of the post-chiral modification of achiral MOF-NH 2as capill...Figure 7.4 (a–d) GC chromatograms based on chiral MOF-based columns to separate ...Figure 7.5 The example of modified MOF with chiral species through postchiral mo...Figure 7.6 Asymmetry unit in Zn-DPYI crystal structure (left). Crystal structure...Scheme 7.1 Synthesis method of chiral [MIL-101(Cr)-tart].Figure 7.7 The preparation steps of one kind of chiral Zn-MOF through post-synth...Scheme 7.2 Interactions in the preparation of [MIL-101(Cr)-tart].Scheme 7.3 The preparation steps of post-chiral modification NU-1000 by SALI met...

8 Chapter 8Figure 8.1 A plot based on the number of published articles about the defect of ...Figure 8.2 MOF with interpenetration [76].Figure 8.3 Different cases of MOFs with various mixed linkers. (a) The parent MO...Figure 8.4 MIL to different forms: (a) without any defect, (b) dangling organic ...Figure 8.5 Defective UiO-66(Zr)-(OH) 2framework for CO 2capture [82].