The Chemistry of Metal-Organic Frameworks E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1711

Veröffentlichungsjahr: 2016

Beschreibung

Providing vital knowledge on the design and synthesis of specific metal-organic framework (MOF) classes as well as their properties, this ready two-volume reference summarizes the state of the art in chemistry. Divided into four parts, the first begins with a basic introduction to typical cluster units or coordination geometries and provides examples of recent and advanced MOF structures and applications typical for the respective class. Part II covers recent progress in linker chemistries, while special MOF classes and morphology design are described in Part III. The fourth part deals with advanced characterization techniques, such as NMR, in situ studies, and modelling. A final unique feature is the inclusion of data sheets of commercially available MOFs in the appendix, enabling experts and newcomers to the field to select the appropriate MOF for a desired application. A must-have reference for chemists, materials scientists, and engineers in academia and industry working in the field of catalysis, gas and water purification, energy storage, separation, and sensors.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

List of Contributors

Chapter 1: Introduction

Chapter 2: Network Topology

2.1 Introduction

2.2 Crystal Structures and MOFs Regarded

as Nets

2.3 Some Introductory Remarks about Graphs, Topology, and Symmetry

2.4 Nomenclature of and Symbols for Nets – or What Does 4.4.4.4.4.4.4.4.4.4.4.4.*.*.* Mean?

2.5 Characterization of Nets in the Spirit of the RCSR

2.6 Derived Nets: Relationships Between Nets

2.7 Simplification of MOFs and Linkers or the Famous Case “4-c versus 2 Times 3-c”

2.8 A Very Short Survey on Common and Not So Common Nets: The Minimal Transitivity Principle

2.9 Summary and Conclusions

Acknowledgment

References

Part I: MOF Chemistry of Metallic Clusters and Other Nodes

Chapter 3: Reticular Chemistry of Metal–Organic Frameworks Composed of Copper and Zinc Metal Oxide Secondary Building Units as Nodes

3.1 Introduction

3.2 Secondary Building Units (SBUs): The Design Principles of MOFs

3.3 Points of Extension

3.4 Concluding Remarks

Acknowledgment

References

Chapter 4: Alkaline Earth Metal-Based Metal–Organic Frameworks: Synthesis, Properties, and Applications

4.1 Introduction

4.2 Synthesis

4.3 Structures

4.4 Properties and Applications

4.5 Conclusions and Outlook

Acknowledgments

References

Chapter 5: Synthesis, Structure, and Selected Properties of Aluminum-, Gallium-, and Indium-Based Metal–Organic Frameworks

5.1 Introduction

5.2 Properties of Al

3+

, Ga

3+

, and In

3+

ions

5.3 Synthesis and Characterization of G13-MOFs

5.4 Prevalent Framework Structures and Inorganic Building Units in G13-MOFs

5.5 Selected G13-MOFs

5.6 Selected Aspects of G13-MOFs

References

Chapter 6: Group 4 Metals as Secondary Building Units: Ti, Zr, and Hf-based MOFs

6.1 Introduction

6.2 Zirconium-Based MOFs

6.3 Summary and Conclusions

References

Chapter 7: Iron and Groups V- and VI-based MOFs

7.1 Introduction: The Chemistry in Solution

7.2 MOFs Based on Iron, Chromium, or Vanadium

7.3 MOFs Based on Nb, Ru, Mo, and W

7.4 Synthesis at the Nanoscale

7.5 Properties

7.6 Conclusion

Acknowledgments

References

Chapter 8: Platinum Group Metal–Organic Frameworks

8.1 Introduction

8.2 Single Node Frameworks

8.3 Metalloligands for the Construction of Mixed Metal–Organic Frameworks (M′MOFs)

8.4 Hofmann-Type MOFs

8.5 Coordination Polymers with Paddle-Wheel Metal Clusters

8.6 Summary and Conclusions

References

Chapter 9: Group 3 Elements and Lanthanide Metals

9.1 Introduction

9.2 Chemistry and Structures of Group 3 and Lanthanide-Based MOFs

9.3 Electronic and Optical Properties of Group 3 and Lanthanide-Based MOFs

9.4 Summary and Conclusions

References

Part II: Functional Linkers

Chapter 10: Extended Linkers for Ultrahigh Surface Area Metal–Organic Frameworks

10.1 Introduction

10.2 Brief Introduction of the History of Porous MOFs

10.3 General Synthetic Strategy for Extended Organic Linkers

10.4 Case Studies of Extended Linkers

10.5 Summary and Conclusions

Acknowledgment

References

Chapter 11: Porous Metal Azolate Frameworks

11.1 Introduction

11.2 Imidazolate Coordination Modes

11.3 Pyrazolate Coordination Modes

11.4 Triazolate Coordination Modes

11.5 Tetrazolate and Other Coordination Modes

11.6 Summary and Conclusions

Acknowledgments

References

Chapter 12: Functional Linkers for Catalysis

12.1 Introduction: MOF in Catalysis

12.2 Self-Assembled Frameworks

12.3 Postsynthetic Modification

12.4 Relevant and Accurate Characterizations as Key for the Design of MOF Catalyst

References

Chapter 13: Chiral Linker Systems

13.1 Introduction

13.2 Section A: Classes of Chiral Linkers

13.3 Section B: Enantioselective Separation and Chromatography with Chiral MOFs

13.4 Summary and Conclusions

References

Chapter 14: Functional Linkers for Electron-Conducting MOFs

14.1 Introduction

14.2 Methods for Measuring Electrical Properties

14.3 Linkers

14.4 Conclusion and Perspective

Acknowledgments

References

Chapter 15: Linkers with Optical Functionality

15.1 Linker Electronic Structure

15.2 Design Principles

15.3 Linkers for Light Harvesting

15.4 Bioimaging

15.5 Linkers for Chemical Sensing

15.6 Radiation Detection

15.7 Conclusions

References

Part III: Special MOF Classes and Morphology Design of MOFs

Chapter 16: Nanoparticles

16.1 Introduction

16.2 Nanoparticles

16.3 Synthesis of MOF Nanoparticles

16.4 Engineering MOF Nanoparticles

16.5 Application of MOF Nanoparticles

16.6 Nanotoxicology

16.7 Summary and Conclusions

Acknowledgments

References

Chapter 17: SURMOFs: Liquid-Phase Epitaxy of Metal–Organic Frameworks on Surfaces

17.1 Introduction

17.2 Fabrication of Novel MOF Materials by LPE-Based Synthesis

17.3 Heterostructured SURMOFs (Hetero-SURMOFs)

17.4 Postsynthetic Modification of SURMOFs

17.5 SURMOFs as New Investigation Platform to Determine MOF Properties

17.6 Advanced Applications

17.7 Conclusion

References

Chapter 18: Granulation and Shaping of Metal–Organic Frameworks

18.1 Introduction

18.2 Granulation

18.3 Spray Drying

18.4 Extrusion

18.5 Pressing

18.6 Summary

Acknowledgments

References

Part IV: Progress in Advanced Characterization of MOFs

Chapter 19: Adsorption Methodology

19.1 Introduction

19.2 Sample Preparation for Adsorption Measurements

19.3 Porosity Determination

19.4 Enthalpy of Adsorption and Isosteric Enthalpy of Adsorption

19.5 High Pressure Adsorption: Fundamentals and Practical Aspects

19.6 Summary and Conclusions

References

Chapter 20: Nuclear Magnetic Resonance of Metal–Organic Frameworks (MOFs)

20.1 Solid-State NMR Spectroscopy: A Brief Introduction

20.2 Applications of Solid-State NMR Spectroscopy to Study the MOF Lattice

20.3 NMR Spectroscopic Studies of Host–Guest Interactions

20.4 Summary and Conclusions

References

Chapter 21: Electron Paramagnetic Resonance

21.1 Introduction

21.2 EPR Spectroscopy

21.3 Applications of EPR in MOF Science

21.4 Conclusions

References

Chapter 22: IR and Raman Spectroscopies Probing MOFs Structure, Defectivity, and Reactivity

22.1 Introduction

22.2 Raman and IR Spectroscopy to Check the Synthesis Product

22.3 Spectroscopic Monitoring of Gas Adsorption

22.4 Spectroscopic Monitoring of Catalytic Reactions

22.5 Conclusions

References

Chapter 23: In Situ X-ray Diffraction and XAS Methods

23.1 Introduction

23.2

In Situ

Diffraction Techniques

23.3

In Situ

X-ray Absorption Spectroscopy on MOFs

23.4 Summary and Conclusions

References

Chapter 24: In Situ Studies of the Crystallization of Metal–Organic Frameworks

24.1 Introduction

24.2

In Situ

Diffraction

24.3 In Situ Studies Using Scattering and Spectroscopic Methods

24.4 Microscopy and Other Methods

24.5 Summary and Future Directions

References

Chapter 25: Role of Molecular Simulations in the Field of MOFs

25.1 Introduction

25.2 Structure Solution of MOFs: An Indispensable Interplay Between Characterization and Modeling Tools

25.3 Structure Prediction of Novel MOFs: A Relatively Poor Success of the High-Throughput Computational Approach

25.4 Adsorption in MOFs: From Prediction Toward Understanding

25.5 Rationalization of the Adsorption Performances of MOFs: A Recent Evolving Field

25.6 Probing the Dynamics of Guests Confined in MOFs Using a Joint Experimental Modeling: A Success Story

25.7 New Computational Challenges

Acknowledgments

References

Chapter 26: Defects and Disorder in MOFs

26.1 Introduction

26.2 Defects in MOFs

26.3 Summary and Conclusions

References

Appendix A: Appendix A: MOF Suppliers

Appendix A: Appendix B: Datasheets

2.1 Aluminum Fumarate (Basolite A520)

2.2 MIL-100(Al) (Material of Institute Lavoisier-100)

2.3 MIL-101(Cr) (Chromium(III) Terephthalate, Material of Institute Lavoisier-101)

2.4 HKUST-1 (Hong Kong University of Science and Technology-1)

2.5 ZIF-8 (Zeolitic Imidazolate Framework-8)

2.6 UiO-66 (Universitetet i Oslo 66, Zirconium Terephthalate)

2.7 DUT-67(Zr) (Dresden University of Technology-67)

Index

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Guide

Cover

Table of Contents

Begin Reading

List of Illustrations

Chapter 2: Network Topology

Figure 2.1 Some examples of different kinds of graphs. (a) A finite, non-simple graph with directed edges, a “loose end”, and a loop; (b) a finite, non-simple graph with multiple connections between some vertices, and (c) an infinite, 2-periodic, simple graph; the black line indicates the repeating unit cell.

Figure 2.2 (a) Three representations of a 3-c net that are geometrically different but topologically identical, because they can be transformed into each other without breaking (and reconnecting) edges. (b) Three identical graphs in which the vertices have identical connections to other vertices (1 is always connected to 2 and 12 and so on) but that have different topological realizations.

Figure 2.3 Three different ways of building 3-periodic nets with uninodal 4-c vertices only: (a) the

dia

net, with tetrahedrally coordinated vertices, (b) the

nbo

net, and (c) the

lvt

net, the latter two with square-planar coordinated vertices;

nbo

and

lvt

are represented in their augmented versions (

-a

).

Figure 2.4 The five Platonic solids (a), the three 2-periodic nets

sql

,

hcb

, and

hxl

as well as the tiling of the

pcu

net (b), together with their respective Schläfli symbols.

Figure 2.5 The vertex symbols of (a) a cuboctahedron, (b) a square pyramid, and (c) the 2-periodic tetranodal (3,3,3,3)-c net

hnc

. Note that the VS 5.5.7 (not 5.7.5) is the result of the cyclic order, which ensures that the direction with a sequence of smallest possible numbers is chosen.

Figure 2.6 In 3-periodic nets an angle can be involved in more than one ring. (a) The red–gray striated angle of the depicted section of the

dia

net is involved in two six-membered rings simultaneously, highlighted in red. (b) The six angles of 4-c vertices are grouped in three pairs of opposite angles (those that do not share an edge).

Figure 2.7 The three pairs of opposite angles together with their rings in which they are involved in the

dia

net. For each angle there are two rings that meet at one vertex.

Figure 2.8 Part of the

pcu

net. (a–c) The 12 four-membered rings that meet at the orange vertex. For the three 180° angles of that vertex, there are no shortest rings, as exemplified for one 180° angle (edge

a

,

b

) in (d) because the purple 6-cycle contain a potential shortcut to the home vertex.

Figure 2.9 Part of the uninodal 2-periodic net

fxt

. The vertex symbol is based on shortest rings (a), which gives 4.6.12, while the point symbol is derived from shortest cycles; for the angle comprising edge

b

,

c

, the shortest possible closed cyclic path is an eight-membered cycle – shown in green; therefore the point symbol is 4.6.8 (b).

Figure 2.10 The tiling of Zeolite A (

lta

), which is composed of double 4-rings (green; face symbol [4

6

]), truncated octahedra (orange; face symbol [4

6

.6

8

]), and truncated cuboctahedra (blue; face symbol [4

12

.6

8

.8

6

]).

Figure 2.11 Screenshot of the

dia

entry of the RCSR.

Figure 2.12 The repeating unit (blue vertices) and their pairs of topological neighbors in the +[

uvw

] and −[

uvw

] directions of the net

pcu

(a),

dia

(b), and

pts

(c). If the topological partners are joined by an arc, then an

n

-handled body is formed.

n

is the genus of that net.

Figure 2.13 Spanning trees (vertices plus blue edges plus blue “loose ends”) that correspond to the repeating unit of a net, the red “handles,” and the resulting quotient graphs of

pcu

(a),

dia

(b), and

pts

(c). The number of “holes” (closed areas bordered by lines/arcs) is the genus of the net.

Figure 2.14 Illustration of the coordination sequence of

sql

up to the fourth coordination shell cs

4

, 4, 8, 12, 16.

Figure 2.15 Illustration of the tiling of the

dia

net. Four faces (a) build one tile (b), which are then face-to-face connected (c). The tiling carries the

dia

net by its edges and vertices (d).

Figure 2.16 Two examples of nets in their basic and augmented versions (

-a

).

Figure 2.17 Part of the structure of the indium sulfide compound ASU-31, in which supertetrahedra of degree three are arranged in a

sod-a-a-a

net, building large cavities (shown as golden sphere) [40].

Figure 2.18 Two possible simplifications of MIL-47/53. (a)

sra

: The double zigzag ladder-type motif is highlighted in magenta (see text). The vertices are 4-c, with three connections within this ladder and one via the linker to a neighboring rod of corner-shared MO

6

octahedra. (b)

rna

: The linker can also be regarded as a twofold 3-c vertex (highlighted again in magenta) and the MO

6

octahedra as 6-c vertices.

Figure 2.19 (a) The linker of MOF-505 can be represented either as a single square-planar node (b) or as two coplanar triangular nodes (c), which together with the square-planar paddle-wheel unit (d) give rise to an

nbo

(e) or

fof

(f) net. Likewise the linker of the Zn paddle-wheel-based DUT-11 (g) can be regarded as a single tetrahedron (h) or two triangular nodes, oriented perpendicular to each other (i), which result in a

pts

(j) or

sur

(k) net, respectively (all nets are shown in their augmented variants).

Figure 2.20 The six nets derived from the parent

pts

net by splitting either the 4-c tetrahedral node into two 3-c nodes or the 4-c square-planar node into two 3-c nodes; all nets are shown in their augmented version (

-a

).

Chapter 3: Reticular Chemistry of Metal–Organic Frameworks Composed of Copper and Zinc Metal Oxide Secondary Building Units as Nodes

Figure 3.1 Selected M−O or M−N clusters that can serve as SBUs in MOFs and are made from zinc and copper;

n

-c describes the connectivity of the node. Color code: black, C; red, O; green, N; purple, Cl; and blue polyhedra, Zn, Cu (PZ, pyrazolate; AD, adeninate; CDC, 9

H

-carbazole-3,6-dicarboxylate; and

m

BDC, 1,3-benzenedicarboxylate). The yellow ball represents the free space in the building unit.

Figure 3.2 Single-crystal X-ray structure of PNMOF-3 along [001]. The hexagonal channels of 14.9 Å in diameter are clearly visible. Hydrogen atoms are omitted for clarity. NH

2

groups are disordered over four positions with occupancy 1/4. Color code: black, C; red, O; green, N; and blue polyhedra, Zn.

Figure 3.3 Combination of Cu

3

(OH)(−PZ)

3

X

3

(X = Cl, OH) and the linear BTR linker that generates an overall 3-c

srs

net. The structure and the underlying

srs

net (augmented version) are shown along [111]. Interpenetrating networks and hydrogen atoms are omitted for clarity. Color code: black, C; red, O; green, N; purple, Cl; and blue polyhedra, Cu.

Figure 3.4 View of the desolvated MOF-2 structure along the crystallographic [001] direction; the rectangular channels are clearly visible. Hydrogen atoms and solvent molecules are omitted for clarity. Color code: black, C; red, O; and blue polyhedra, Zn.

Figure 3.5 Gas adsorption isotherm for MOF-2 probed with nitrogen at 77 K. This served as the first example of microporosity reported in an MOF.

Figure 3.6 Single-crystal X-ray structure of the guest-free (tetragonal) form of MOF-11. The Cu-paddle wheels display open metal sites (OMSs) pointing into the interior of the pore. Augmented

pts

net, consisting of squares and tetrahedra in a ratio of 2 : 1 (right). Color code: black, C; red, O; and blue polyhedra, Cu. The yellow ball represents the empty space in the framework.

Figure 3.7 The combination of Cu

2

(−COO)

4

and BTC affords HKUST-1. The underlying topology is a 3,4-c

tbo

net. Hydrogen atoms and solvent molecules are omitted for clarity. Color code: black, C; red, O; and blue, Cu. The yellow and orange balls represent the empty space in the framework.

Figure 3.8 The

nbo

/

fof

net (MOF-505) sustained by a tetracarboxylate linker. The overall structure can be viewed as linker-to-linker cross-linked hexagonal kagomé (

kgm

) layers that are in turn built from Cu

2

(−COO)

4

paddle-wheel SBUs and

m

BDC moieties. Hydrogen atoms are omitted for clarity. Color code: black, C; red, O; and blue, Cu. The yellow ball represents the empty space in the framework.

Figure 3.9 Single-crystal X-ray structure of MOF-3. Three octahedrally coordinated Zn

2+

that are bridged by a total of six carboxylates form a distorted octahedral SBU (red) which also contains terminal MeOH ligands. Linking of these SBUs together by BDC affords MOF-3 with

pcu

topology. Color code: black, C; red, O; blue octahedra, Zn; and red octahedron, vertex figure.

Figure 3.10 The three-dimensional structure of MOF-5. The two cavities are highlighted in yellow and orange, respectively. Color code: black, C; red, O; and blue tetrahedra, Zn.

Figure 3.11 Gas adsorption isotherm of MOF-5 probed with nitrogen at 77 K. The graph clearly shows a type I isotherm, indicative of a microporous material.

Figure 3.12 Partial replacement of the carboxylate moieties through pyrazole- (PZ) type linkers. The coordination complements the carboxylate motif in a 2 : 1 ratio. Mixed Zn

4

O(BDC)(BPZ)

2

viewed along [100]; the underlying

pcu

net is clearly visible. Color code: black, C; red, O; and blue tetrahedra, Zn.

Figure 3.13 Single-crystal X-ray structure of UMCM-150. Cu-paddle wheel and trigonal prismatic clusters together with a desymmetrized tricarboxylate linker sustain the 3,4,6-c

agw

net. Alternating layers of undulating kagomé (

kgm

) and trigonal prisms are clearly visible. Color code: black, C; red, O; and blue polyhedra, Cu.

Figure 3.14 Single-crystal X-ray structure of the Cu-BTT-MOF along [100] (left). The underlying topology a 3,8-c

the

net is represented as the augmented version

the-a

. Color code: black, C; green, N; purple, Cl; and blue polyhedra, Cu. The yellow ball represents the open space in the framework.

Figure 3.15 MOF built from Cu

4

Cl(−COO)

8

SBUs that are in turn connected by BTC linkers. If each Cu

2+

ion is considered as a tetrahedral node of the underlying topology, a

sod

net is obtained. Color code: black, C; green, N; purple, Cl; and blue polyhedra, Cu. The yellow ball represents the open space in the framework.

Figure 3.16 An unusual 9-c trinuclear Zn

3

O(−COO)

6

(−PY)

3

SBU, when reacted with the chiral linker d-HDMPDC, affords POST-1 that is composed of two-dimensional undulating hexagonal layers (

hcb

). The pores are running along [001] and provide space for catalytic, enantioselective transesterification reactions in their interior. Color code: black, C; green, N; and blue polyhedra, Zn.

Figure 3.17 Double-walled

pcu

net built of Zn

8

(SiO

4

)(−COO)

12

SBUs together with BDC. The interpenetrating net and hydrogen atoms are omitted for clarity. Color code: black, C; red, O; blue tetrahedra, Zn; and pink tetrahedra, Si.

Figure 3.18 12-c Zn

8

O

2

(AD)

4

(−COO)

12

ZABU that serves as an overall truncated tetrahedron. Each ZABU is triple cross-linked with BPDC to afford bio-MOF-100. Hydrogen atoms are omitted for clarity. Color code: black, C; red, O; green, N; and blue tetrahedra, Zn.

Figure 3.19 Difference between

dia

,

lon

, and

lcs

topology nets (from (a) to (c)). The chair conformation in

dia

and the boat conformation in

lon

are clearly visible. The

lcs

topology consists of a twist boat which rotates the six-membered rings along [001] by an angle of 60° with respect to each other.

Figure 3.20 Construction of MOP-1 and its possibilities to serve as a 12-c

cuo

-node through functionalization of open metal sites or as a 24-c

rco

-node through extension of the

m

BDC-linker at its 5-position. Color code: black, C; red, O; green, N; and blue polyhedra, Cu. The yellow ball represents empty space in the building unit.

Figure 3.21 View of the 12-c polyhedral structure of the

fcu

net along [110]. Each MOP-15 is connected to 12 others via ditopic BIPY linkers. Color code: black, C; red, O; green, N; and blue polyhedra, Cu. The yellow ball represents empty space in the framework.

Figure 3.22 Quadruple cross-linking of metal–organic polyhedra into an

mjz

net that could be further simplified to an overall

pcu

net. Only one net of the twofold interpenetrated structure is shown, and hydrogen atoms are omitted for clarity. Color code: black, C; red, O; and blue, Cu. The yellow ball represents the empty space in the framework.

Figure 3.23 Schematic of

rht

-MOF-1 sustained by a Cu

24

(−

m

BDC)

24

(

rco

) building block together with a triangular Cu

3

O(−PZ)

3

. The underlying topology (

rht

) is the only 3,24-c net possible as predicted. Hydrogen atoms are omitted for clarity. Color code: black, C; red, O; green, N; and blue polyhedra, Cu. The yellow and orange balls represent empty space in the framework.

Figure 3.24 Modularity of the

rht

net: The original MOP-1 is isoreticular expanded leading to the recently reported

rht

-MOF-2 (bottom, right). Isoreticular expansion of the triangular linker (here using a phenyl moiety) results in the highly porous NU-110. Color code: black, C; red, O; green, N; and blue polyhedra, Cu. The yellow and orange balls represent empty space in the framework.

Figure 3.25 Schematic of linking a discrete

cuo

-MOP Cu

12

(−CDC)

12

with linear linkers (DUT-49) or square nodes (DUT-75). High surface area materials with either

fcu

or

ftw

topology were afforded. Color code: black, C; red, O; green, N; and blue polyhedra, Cu. The yellow and orange balls represent empty space in the framework.

Figure 3.26 Parent MOF-74 Zn

2

(DOT)(DMF)

2

·2H

2

O viewed along [001]. The hexagonal channels are clearly visible. Rodlike building units of formula [Zn

2

(−O)

2

(−COO)

2

]

∞

that are linked together by DOT spawn a

bnn

(shown here) or

etb

net, respectively. Color code: black, C; red, O; and blue polyhedra, Zn.

Figure 3.27 Infinite secondary building unit [Zn

8

O(AD)

4

(−COO)

12

]

∞

that sustains bio-MOF-1 (viewed along [001]). Color code: black, C; red, O; green, N; and blue polyhedra, Zn.

Chapter 4: Alkaline Earth Metal-Based Metal–Organic Frameworks: Synthesis, Properties, and Applications

Figure 4.1 (a) A view of the two interpenetrating frameworks of BCF-3 along the [010] direction. (b) A view of the framework structure of BCF-4 along the [110] direction.

Figure 4.2 Different modifications of magnesium formates: (a) α-form along the [010] direction, (b) β-form along the [010] direction, and (c) γ-form along the [100] direction.

Figure 4.3 (a) Crystal structure of Mg

2

(dobdc) (MOF-74-Mg) (

1

) and Mg

2

(dobpdc) (

2

) along crystallographic

c

-axis. (b) A close-up of the open metal sites that interact with the guest species.

Figure 4.4 The formation of different types of Mg-pdc (3,5-pyridinedicarboxylate(pdc)) based on different synthesis solvents.

Figure 4.5 (a) The connectivity of Ca(sdb) along crystallographic [010] direction. (b) Structural difference between as-synthesized (top) and activated (bottom) material, showing cross section of the channel and parallel organization of organic linkers.

Figure 4.6 (a) The crystal structure of Be

12

(OH)

12

(btb)

4

along crystallographic [001] direction. (b) H

2

adsorption isotherm at 77 K (blue) and 87 K (green).

Figure 4.7 CO

2

adsorption isotherm (296 K, 0–1 atm) of MOF-74-M series, along with an insert of the low-pressure region from 0 to 0.1 atm.

Figure 4.8 (a) The interaction of adsorbed CO

2

molecules with impregnated amine molecules (green, magnesium; red, oxygen; and gray, carbon atoms). (b) The adsorption of CO

2

in mmen impregnated MOF at 25 °C (blue squares), 50 °C (green triangles), and 75 °C (red circles).

Figure 4.9 (a) Local environment of the adsorbed CO

2

(blue spheres, calcium; red, oxygen; black, carbon; and yellow, sulfur). (b) CO

2

adsorption–desorption isotherms at 273 K (black), 288 K (red), and 298 K (blue). (b) Heats of adsorption (

Q

st

) for CO

2

and N

2

calculated on the basis of the Virial method. (a) Local environment of adsorbed CO

2

in Ca(sdb).

Figure 4.10 (a) Schematic diagram of Mg-ndi crystals showing different colors in different solvents. (b) The color change of the MOF samples in presence of different amines (0.1 M concentration).

Chapter 5: Synthesis, Structure, and Selected Properties of Aluminum-, Gallium-, and Indium-Based Metal–Organic Frameworks

Figure 5.1 Distribution of publications dealing with G13-MOFs (SciFinder

®

, March 14, 2015).

Figure 5.2 Outline of the topics covered within this chapter.

Figure 5.3 Typical IBUs observed in G13-MOFs. I: 8 edge- and corner-sharing octahedra, II: 12 edge-sharing octahedra, III: linear chain of

trans

-corner-sharing octahedra, IV: helical chain of

cis

-corner-sharing octahedra, V: GaO

4

polyhedron, VI: trinuclear [M

3

(μ

3

-O)(−CO

2

)

6

]

+

, and VI: [In(−CO

2

)

4

]

−

– the topology of this node constitutes a distorted tetrahedron. While IBUs I and II have only been observed for Al-MOF, the IBUs V and VII are exclusively found for Ga- and In-MOFs, respectively. The trinuclear IBU VI can be found in MOF structure of all three elements but is significantly rarer for aluminum.

Figure 5.4 Scheme of important MOF structures containing chains of

trans

-corner-sharing MO

6

polyhedra and linear dicarboxylate molecules.

Figure 5.5 The structures of the 3D MOF CAU-8 ([Al(OH)(BPhDC)]) and the 2D MOF CAU-11 ([Al(OH)(SDBA)]). These MOFs are two examples for framework structures based on extended, bent linker molecules and chains of

trans

-corner-sharing MO

6

polyhedra.

Figure 5.6 G13-MOF structures containing chains of edge-sharing MO

6

polyhedra and polycarboxylate molecules with an

ortho

-substitution pattern.

Figure 5.7 Isoreticular G13-MOF structures (MIL-118 type) incorporating

trans

-corner-sharing chains of MO

6

polyhedra and tetracarboxylate molecules. All compounds have the general composition [Al

2

(OH)

2

linker].

Figure 5.8 Building units and framework structure of MIL-96.

Figure 5.9 IBUs, which are unique for G13-MOFs containing aluminum. In addition to the composition and the structure of the IBU, the name of the respective MOF is given.

Figure 5.10 G13-MOFs with the metal ion in the CN = 7 and 8 are unique to indium. With CN = 8 [In(CO

2

)

4

]

−

IBUs are almost exclusively observed, and negatively charged frameworks are formed. Hence structure-directing agents can be employed that can lead to chiral frameworks.

Figure 5.11 Principal types of breathing: (I) flexibility of the IBUs, (II) structural changes of the linker molecules, and (III) shift of interpenetrated or interwoven frameworks.

Chapter 6: Group 4 Metals as Secondary Building Units: Ti, Zr, and Hf-based MOFs

Figure 6.1 Isolated Ti−O clusters.

Figure 6.2 Structure of MIL-125. (a) Ti

8

O

8

(OH)

4

(CO

2

)

12

unit, (b) crystal structure, and (c)

fcu

topology [8].

Figure 6.3 Alcohol oxidation catalyzed by MIL-125 under UV radiation.

Figure 6.4 Photocatalytic CO

2

reduction over NH

2

-MIL-125 under visible light irradiation [11].

Figure 6.5 Schematic illustration of photocatalytic hydrogen production reaction over Pt@NH

2

-MIL-125 [10].

Figure 6.6 The structure of UiO-67, an isoreticular derivative of UiO-66 distinguished by using a biphenyl dicarboxylate (BPDC) organic linker instead of UiO-66's benzene dicarboxylate (BDC) linker.

Figure 6.7 The Zr

6

O

8

can be dehydrated to form a Zr

6

O

6

SBU of identical linker connectivity.

Figure 6.8 Postsynthetic modification of UiO-66-NH

2

(a) with acid anhydrides leads to stoichiometric reaction with the amino functional group. The product formed with acetic anhydride is shown (b).

Figure 6.9 The increased CO

2

uptake of UiO-66 after postsynthetic titanium exchange.

Figure 6.10 UiO-66-modulated synthesis to increase surface area and catalytic activity.

Figure 6.11 UiO-67 prepared with (b) no benzoic acid, (c) 3 equiv. of benzoic acid, and (d) 30 equiv. of benzoic acid.

Figure 6.12 The proportion of missing-linker defects in UiO-66 changes with amount of modulator used.

Figure 6.13 Structural and topological representation of ZrSQU. SQU linkers (a) and Zr

6

O

4

(OH)

4

(C

2

O

2

)

12

clusters (b) stack in an

fcu

-lattice (c), delineating octahedral (orange, d) and tetrahedral (green, e) cages with triangular windows. (Zr, blue; O, red; C, black).

Figure 6.14 A ligand which changes color upon oxidation and reduction makes the MOF containing it act as a sensor for redox-active species.

Figure 6.15 A PtCl

2

immobilizing ligand (a) produces a stable, reactive heterogeneous catalyst when used in a UiO-67 type MOF (b).

Figure 6.16 N

2

ad-/desorption isotherms of H

2

N-UiO-66 before (•) and after (•) the cycling procedure, and of H

2

N-MIL-25 before (□) and after (▿) the cycling procedure. Adsorption is depicted with filled and desorption with empty symbols.

Figure 6.17 (a) Reaction conditions for F-C reaction between indole and β-nitrostyrene. (b) UiO-67-Squar/bpdc (blue) shows drastically improved catalytic activity over UiO-67-Urea/bpdc (green) and UiO-67 (red). The MOF-free control shows no detectable yield (black). Reaction progress was monitored by

1

H NMR spectroscopy. Standard deviation at 24 h determined using multiple synthesized batches of respective MOFs. Product determined to be racemic by chiral HPLC.

Figure 6.18 Hammett plot for oxidation of aqueous As(III) with UiO-66-X (X = H, NH

2

, NO

2

, and Br) catalysts.

Figure 6.19 Topology-guided design of zirconium–porphyrin MOF.

Figure 6.20 Possible vertex Figure of cluster and ligands.

Figure 6.21 (a) Representation of the connections of Zr

6

O

8

and TCPP and the sterically controlled phenyl and carboxylate angle. (b) Substitution of the Zr

6

O

8

cluster and TCPP in

ftw

topology and the chemically forbidden conformation of ligand (highlighted with red circle). (c) Representation of the Zr

6

O

8

and Zr

8

O

6

cluster and the 90° rotation of the carboxylate groups between these two clusters. (d) Structure of PCN-221 constructed with Zr

8

O

6

cluster and TCPP. (e) Structure of PCN-228 constructed with Zr

6

O

8

cluster and TCP-1 (ethyl groups were omitted for clarity).

Figure 6.22 Structure of elongated porphyrinic ligands.

Figure 6.23 Structure of MOFs with elongated porphyrinic ligands.

Figure 6.24 The

shp-a

topology derived from

scu

topology by linker installation.

Figure 6.25 Structure of zirconium porphyrinic MOFs.

Figure 6.26 PIZOF ligands.

Figure 6.27 The PIZOF a) linker, b) secondary building unit, c) structure showing 2 distinct pore sizes, d) connectivity, e) larger pore, f) smaller pore, and g) interpenetrated

fcu

topologies.

Figure 6.28 Shown is the a) Secondary Building Unit, b) ligation of the SBU c) structure with 2 pore sizes, and d) idealized pore structure of DUT-51.

Figure Scheme 6.1 (a) Carboxylic functional groups (CFGs) incorporated through SALI into

NU-1000

and (b) secondary functionalization reactions: (i) “click,” (ii) imine condensation, and (iii) methylation, involving SALI derivatives of

NU-1000

.

Figure 6.30 Molecular representations of NU-1000 (top) and depictions of solvent-assisted ligand incorporation (SALI) (bottom).

Chapter 7: Iron and Groups V- and VI-based MOFs

Figure 7.1 View of STA-12(Fe) crystal structure. Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.2 Typical SBUs from the M

3+

/carboxylate system. (a) [M(OH)(CO

2

)

2

]

n

chain and (b) M

3

O(CO

2

)

6

X(S)

n

trimer. Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.3 Examples of M

3+

polycarboxylate structures. MIL-53, MIL-68, MIL-69, Iron naphthalenedicarboxylate (FeNDC), MIL-71, and MIL-59; MIL-88, MIL-127, MIL-100, MIL-101_NDC, MIL-101_BPDC (biphenyldicarboxylate), and MIL-100_BTB. Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.4 “Unusual” iron or vanadium polycarboxylate MOFs: MIL-85, MIL-141, PCN-333, and Fe-BTB. Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.5 View of the crystal structures of MIL-142A, MIL-143, PCN-264, and PCN-285. Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.6 View of the different metal(III) bis-azolate MOFs: FeBDP (a) and CrClBDT (b). Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.7 View of the CPO-27(Fe) or MOF-74(Fe) crystal structure (a) and metal(II) dioxohydroquinone structures (b). Metal polyhedra and carbon atoms are in gray and black, respectively.

Figure 7.8 (a) Ru(II) phosphonate paddle wheel and (b) structure of MoO

3

(4,4′-bipy)

0.5

.

Figure 7.9 View of the flexible character of MIL-53 (left) and MIL-88B (right).

Figure 7.10 Impact of the functional groups over the flexibility of MIL-88B: evolution of the geometrical features with the steric hindrance of the functional groups.

Figure 7.11 Kinetics of release of the constitutive linker in phosphate buffer solution (PBS), 37 °C for MIL-100(Fe) and MIL-127(Fe) under different media.

Figure 7.12 Schematic view of the bio-MOFs concept.

Figure 7.13 Examples or redox-driven insertions.

Figure 7.14 Adsorption isotherms of various CO

2

–CH

4

mixtures in MIL-53(Cr) at 303 K.

Figure 7.15 Breakthrough curves on an equimolar binary mixture (

P

= 0.25 kPa) of propane and propene in MIL-100(Fe) after activation at 150 °C (squares) and 250 °C (circles).

Chapter 8: Platinum Group Metal–Organic Frameworks

Figure 8.1 Representation of (a) the square-planar coordination environment of the Pd centers; (b) the three structural motives present in the crystal structures of the hydrated and the anhydrous forms of [Pd(F-pymo)

2

], namely, planar molecular hexagon (1), metallacalix[4]arene (2), and metallacalix[6]arene (3); and (c) the 3D sodalitic framework, where the vertices are the metal centers and the edges represent the bridging ligands. (d) Consumption of hydrogen during the [Pd(H-pymo)

2

]·3H

2

O-catalyzed hydrogenation of 1-octene and cyclododecene in the liquid phase. Arrows mark reaction times of 40 min and 3.6 h.

Figure 8.2 (a) Schematic illustration for the formation of a metal–organic nanotube using polymerization of metal–organic building blocks. (b) The square prism-shaped tubular structure determined by single-crystal X-ray crystallography. (c) Possible “CDW quartets” of the MX tube based on the group-theoretical bifurcation theory, where Pt(II), Pt(III), Pt(IV), and I- are shown by green, blue, red, and yellow spheres, respectively. The notation +, −, or 0 in the CDW quartets denotes the charges relative to Pt(III) on adjacent platinum ions forming a square section of MX tube. (d) Single-crystal

c

-axis-polarized optical conductivity spectrum. (e) Two types of “quartet” of MX chains composed of the intratube (blue) and intertube (red) correlations as candidates to form “CDW quartets” in the crystal structure, where adjacent chain distances are 11.168 (intratube) and 8.726 Å (intertube), respectively.

Figure Scheme 8.1 Metalloligand approach for the construction of mixed metal–organic frameworks (M′MOFs).

Figure 8.3 Zirconium amorphous chiral MOFs based on BINAP functionalized with phosphonate residues (a) and crystalline MOF based on BINAP systems functionalized with carboxylate residues (b).

Figure 8.4 Synthesis and single-crystal to single-crystal reduction/oxidation of 1 and 2. The photographs illustrate the typical colors and morphologies of 2 (green) and 2R (red).

Figure 8.5 (a) Strategy for the obtention of LRuZn M′MOF. (b) X-ray crystal structure of the LRuZn M′MOF showing the side view of a 2D bilayer along the

b

-axis and energy transfer from Ru to Os. (c) Transients for 1.4 and 2.6 mol% Os-doped LRuZn M′MOFs at 620 and 710 nm with emission at 620 nm dominated by Ru(II)* and at 710 nm by Os(II)*.

Figure 8.6 (a) Structure of [Pt(nicH)2(nic)2] metalloligand; (b) crystal structure of Cd[Pt(nic)4]; (c) packing view along the

c

-axis; and (d) space-filling model of 2D network structure along the

a–b

plane.

Figure 8.7 TEM and SEM micrographs of silica-coated {Tb

2

[Pt(succinate)

2

(NH

3

)

2

Cl

2

]

3

(H

2

O)

12

] and schematic mechanism of the cisplatin release process.

Figure 8.8 (a) The basic cavity structure of {Fe(pz)[Pt(CN)

4

]·2H

2

O}. (b) Projection of the 3D porous framework of {Fe(pz)[Pt(CN)

4

]·2H

2

O}. (c) The basic cavity structure of {Fe(pz)[Pt(CN)

4

]·CS

2

}. The S2 atom is disordered through the mirror plane on the S1 atom, and one S2 atom is omitted for clarifying. (d) The basic cavity structure of {Fe(pz)[Pt(CN)

4

]·pz}. Fe (orange), Pt (pink), N (blue), C (gray), S (yellow), guest molecules (black except for S atoms); the red and green lines in (c) and (d) are a guide for the eye and indicate the closest contacts between the guest and the framework. (e,f) Temperature dependences of

χ

M

T

for guest-free {Fe(pz)[Pt(CN)

4

]} (blue and GF), benzene clathrate (yellow), CS

2

clathrate (purple), thiophene clathrate (thio), pyrrole clathrate (pyr), and furane clathrate (fur) in the temperature range of 240–350 K. The sample color changed between deep red (LS) and yellow orange (HS) depending on the temperature and guest molecules.

Figure 8.9 (a) X-ray crystal structure showing the phenazine inclusion in the channels of {Fe(dpe)[Pt(CN)

4

]·phenazine} parallel to the [010] direction. (b) Magnetic properties of {Fe(dpe)[Pt(CN)

4

]·G} (G = phenazine, anthracene, and naphthalene) in the form of

χ

M

T

versus

T

. Depending on the size of the aromatic guest molecule included in the framework, spin-crossover (incomplete (anthracene clathrate) or two-step (phenazine derivative)) or paramagnetic behavior (naphthalene clathrate) is observed.

Figure 8.10 (A) Projection of the structure of {Fe(bpb)[Pt(CN)

4

]}·2naphthalene along

a

. Two types of guest naphthalene molecules are colored in red and blue. (B) Magnetic (filled circles) and calorimetric (blue and red lines refer to cooling and heating modes, respectively) measurements for {Fe(bpb)[Pt(CN)

4

]}·2naphthalene (a) and {Fe(bpb)[Pt(CN)

4

]}·2nitrobenzene (b). The naphthalene derivative undergoes spin transition in two equal steps defining two hysteresis loops 11 and 15 K wide. However, in the nitrobenzene clathrate, the transition takes place in one step at with the hysteresis loop at 27 K.

Figure 8.11 Representation of the NO adsorption process in the interchain space of the 1D paddle-wheel [M

2

(4-Cl–2-OMePhCO

2

)

4

(phz)] (M = Ru, Rh) systems (a) and the corresponding NO adsorption isotherms exhibiting gated phenomena and hysteresis loops (b).

Figure 8.12 (a) A view of the honeycomb 2D (6,3) net structure. The ring diagonals are about 20 Å. The phenyl groups of the Ru

2

cores are omitted for clarity. (b) The plane 2D layer architectures are stacked in parallel in ABC alternations. The distance between each layer is about 10 Å. The benzoates of the Ru

2

cores are omitted for clarity. The ruthenium, oxygen, carbon, and nitrogen atoms are denoted by blue, red, gray, and sky blue, respectively.

Figure 8.13 Molecular structure of [Rh

2

(MTCPP)]

n

(M = H, Cu(II), Ni(II), and Pd(II)). Elements are color-coded: Rh, green; C, gray; N, blue; O, red; and M, pink.

Figure 8.14 Defect-engineered [Ru

3

(btc)

2−

x

(pydc)

x

X

y

] (X = Cl, OH, OAc;

x

= 0.1, 0.2, 0.6, 1; 0 ≤

y

≤ 1.5 (left) and parent [Ru

3

(btc)

2

Cl

1.5

] (right).

Chapter 9: Group 3 Elements and Lanthanide Metals

Figure Scheme 9.1 Ln-MOFs and the multifunctionality of relevant properties.

Figure Scheme 9.2 The ionic radii of the trivalent group 3 metal and lanthanide ions Ln

3+

and their steady decrease from La(57) to Lu (71).

Figure 9.1 (a) Ligand and [Nd

4

(μ

4

-CO

3

)] cluster node of the MOF (Me

2

NH

2

)

2·

[Nd

4

(CO

3

)L

4

(DMF)

2

(H

2

O)

2

]·2H

2

O, L = tris(

p

-carboxylato)tridurylborane and (b) the 12-connected 3D framework (Nd, green polyhedra; B, orange; N, blue; O, red; C, gray).

Figure 9.2 Top: The crystal structure of {[Er

2

(PDC)

3

(DMF)

2

]

n

(solv)}

∞

with coordinated DMF molecules protruding into the channels (left) and the crystal structure of [Er

2

(PDC)

3

]

n

after removal of coordinated DMF and solvent molecules upon heating (right).

Figure 9.3 Different structures observed for Ln-MOFs with the acrylamide-modified ligand H

3

BTATC = 4,4′,4″-(benzenetricarbonyltris-(azanediyl))tribenzoic acid) and Ln

3+

with CN = 8 as well as CN = 9, resulting in different acrylamide alignments (O, red spheres; N, blue spheres; and C, gray spheres); open symbols represent desorption. Bottom: Adsorption isotherms of CO

2

, C

2

H

4

, and C

2

H

6

for the Y/Ho (a) and for La (b) at 195 K indicating the selective adsorption correlating with the higher coordination number.

Figure Scheme 9.3 Emission spectra of the trivalent lanthanide ions Sm

3+

, Eu

3+

, Tb

3+

, and Dy

3+

and the correlating 4f transitions observed for the MOF series [134, 135]. The 4f transitions are typical for the relating Ln ions.

Figure Scheme 9.4 Dieke diagram of the Ln

3+

and the relevant 4f–4f transitions for visible luminescence for Sm

3+

, Eu

3+

, Tb

3+

, and Dy

3+

. The emissive levels are marked in red and the 4f ground states in blue.

Figure Scheme 9.5 Relevant luminescence effects in Ln-MOFs based on ligand sensitization: excitation and emission by the organic linker (fluorescence and phosphorescence subsequent to intersystem crossing (ISC), ligand-to-metal energy and charge transfer (LM-ET), metal-to-metal energy transfer, 4f–4f excitation and emission, internal conversion by radiationless decay, inner filter effects by reabsorption of an ligand-based MOF emission, and reemission by Ln ions, 4f–5d-based excitation and emission.

Figure 9.4 The crystal structure of the Ln-MOF series (top) and luminescence colors according to 4f-Ln

3+

emission (middle). Codoping of the MOF series with different Ln

3+

ions adapted for a linear tuning of the chromaticity of the luminescence (bottom).

Figure 9.5 (a) Coordination environments of the BTB ligand and a Gd

3+

ion and (b) crystal structure of [Ln(BTB)(DMSO)

2

]H

2

O. (c) CIE-1931 chromaticity diagram showing the tuning of the emission color of the Ln-MOF [Eu

0.004

Tb

0.046

Gd

0.950

(BTB)(DMSO)

2

]H

2

O from yellow to white and blue by varying the excitation wavelength and (d) the energy transfer efficiency for Tb

3+

→ Eu

3+

as a function of the excitation wavelength.

Figure 9.6 The upconversion process in between Yb

3+

and Tb

3+

in the MOF [(Tb

1−

x

Yb

x

)·(DPA)(HDPA)] (top); trace marker emission spectra (a), unmarked ammunition (b), UC-Marker 1 ammunition after usage (c), images of residues with trace markers under visible light (d), and excitation radiation (e).

Figure 9.7 Crystal structure of [Eu

3

(MFDA)

4

(NO

3

)(DMF)

3

] (top left, hydrogen atoms and terminal DMF molecules omitted for clarity); quenching percentage of the Eu

3+

luminescence for different organic nitro compounds (bottom left); concentration-dependent luminescence quenching (dispersion in DMF) after adding different concentrations of (a) 3,4-DNT, (b) 1,2-DNB, and (c) 2,4-DNT (right, excited at 336 nm at room temperature. Insets: Stern–Volmer plots).

Figure 9.8 (a) Crystal structure of the MOF ; (b) blue luminescence of nonactivated and activated MOF; (c) respective excitation and emission spectra of the nonactivated and activated MOF; (d) emission spectra with immediate quenching upon contact to water (

t

1/2

to reach

λ

max

= 3 s); (e) gas-dependent adsorption (BET); and (f) time-dependent intensity decrease for contact with air components.

Figure 9.9 (a) The temperature-dependent color shift of the MOF [(Eu

x

Tb

1−

x

)

2

(DMBDC)

3

(H

2

O)

4

] from green at 10 K to red at 300 K and (b) temperature-dependent emission spectra and the referring luminescence color impression.

Chapter 10: Extended Linkers for Ultrahigh Surface Area Metal–Organic Frameworks

Figure 10.1 Crystal structures of highly porous MOFs. Chemical formula and BET surface areas are given for each MOF. The yellow and orange spheres are placed in the structure to indicate space in the cage. Atom colors: C, black; O, red; N, green; Zn or Cr metal, blue polyhedra; Cu, blue squares. Hydrogen atoms are omitted for clarity.

Figure 10.2 Possible combination of the core (top) and extending units (left) to form extended organic structures (carboxylate ester terminals are shown in filled circles). These terminals are converted to carboxylic acids to introduce binding sites (Y-shaped anchors in bottom).

Figure Scheme 10.1 Retrosynthetic analysis of a tetratopic H

4

ETTC. The white arrows denote the transfer of a target molecule to its synthetic precursors.

Figure Scheme 10.2 Examples of linear (top) and branched (bottom) extending units. B(pin) = (pinacolato)boron.

Figure Scheme 10.3 Three typical palladium-catalyzed coupling reactions to construct linker backbones. B(pin) = (pinacolato)diboron; OTs = 4-toluenesulfonate; and OTf = trifluoromethanesulfonate.

Figure Scheme 10.4 Three examples of how binding sites can be incorporated within linkers.

Figure Scheme 10.5 Representative ditopic linkers used to construct MOFs.

Figure Scheme 10.6 Representative tritopic linkers used to construct MOFs.

Figure Scheme 10.7 Representative tetratopic linkers used to construct MOFs. A polyhedron in H

4

CBI represents

p

-carborane.

Figure Scheme 10.8 A rare example of a pentatopic linker used for MOF construction.

Figure Scheme 10.9 Representative hexatopic linkers used to construct MOFs.

Figure Scheme 10.10 Representative octatopic linkers used to construct MOFs.

Figure Scheme 10.11 Representative dodecatopic linkers used to construct MOFs.

Chapter 11: Porous Metal Azolate Frameworks

Figure 11.1 (a) Structures of five types of azolates and (b) comparison of the typical coordination modes of azolate and carboxylate groups (X = C−H or N).

Figure 11.2 Simplified structures of (a) SOD-[Zn(bim)

2

], (b) RHO-[Zn(bim)

2

], and (c)

sql

-[Zn(bim)

2

], as well as (d) the open/close transformation of SOD-[Zn(bim)

2

].

Figure 11.3 The

dia

network structure of MAF-66.

Figure 11.4 Construction of MAF-35 by linking two types of square-planar building blocks.

Figure 11.5 The simplified

gie

topology of [Zn(bimh)].

Figure 11.6 Single-crystal structures of (a) MAF-23 and (b) MAF-23·1.5CO

2

measured at 195 K. Hydrogen atoms are omitted for clarity. Short intermolecular contacts are shown as dashed lines.

Figure 11.7 Simplified structures of (a) [Zn(bttz)] and (b) [Zn(Hdttz)].

Figure 11.8 Linking triangular M

3

(pz)

3

clusters by mbpz

2−

ligands to form isomers with

nof

and

srs

topologies (interpenetration is omitted for clarity).

Figure 11.9 Linking triangular M

3

(pz)

3

clusters by pbpz

2−

ligands to form isomers with

srs

and

hcb

topologies (interpenetration and stacking are omitted for clarity).

Figure 11.10 Linking triangular M

3

(pz)

3

and tetradedral M

4

(pz)

4

clusters by ebpz

2−

ligands to form a 3,4-connected porous network (interpenetration is omitted for clarity).

Figure 11.11 Linking octahedral Zn

4

O(pz)

4

(COO)

2

clusters by mbpz

2−

and linear dicarboxylate ligands to form elongated

pcu

networks.

Figure 11.12 Linking the octahedral Zn

4

O(pz)

3

(COO)

3

clusters by linear pyrazolate–carboxylate ditopic ligands to form regular

pcu

networks.

Figure 11.13 Linking the octahedral Co

4

O(pz)

6

clusters by linear bipyrazolate ligands to form regular

pcu

networks.

Figure 11.14 Linking the tetragonal-prismatic clusters by linear, triangular, and square-planar polypyrazolates to form porous frameworks with (a) 8-connected

bcu

, (b) 3,8-connected

the

, and (c) 4,8-connected

scu

topologies.

Figure 11.15 Linking the cubic 12-connected [Ni

8

(μ

4

-OH)

4

(μ

4

-H

2

O)

2

(pz)

12

] clusters by linear bipyrazolate ligands or pyrazolate–carboxylate ligands to form

fcu

networks.

Figure 11.16 Framework structures of (a) [Zn(bpz)], (b) [Zn(mpbz)], (c) [Zn(bdp)], (d) [Co(mbdp)], and (e) [Zn(bpeb)].

Figure 11.17 The 3D pillared-column framework structure of MAF-X8 viewed along the channel direction.

Figure 11.18 Framework structures of (a) [Ni(bpz)], (b) [Ni(bdp)], and (c) [Ni(bpeb)].

Figure 11.19 Linking the fourfold symmetric M(pz)

2

chains by triangular polyprazolate to form a 3D open framework.

Figure 11.20 Linking the sixfold symmetric M(pz)

3

chains by linear polyprazolate-type ligands (a) bdp

2−

, (b) bpeb

2−

, and (c) bdttz

2−

to form a 3D open framework with triangular- or quadrilateral-shaped 1D channels.

Figure 11.21 (a) Crystal structure (ethyl groups are omitted for clarity), (b) luminescence decay profile, (c) Stern–Volmer plot, and (d) interfacial crystal growth method for MAF-2.

Figure 11.22 (a) Framework breathing, (b–d) single-crystal structures of as-synthesized, O

2

-loaded, and oxidized states, and (e) aerobic oxidization mechanism of MAF-42.

Figure 11.23 Framework structures of (a) MFU-4, (b) MFU-4

l

, and (c) CFA-1.

Figure 11.24 Stepwise postmodification synthesis of Cu

I

-MFU-4

l

from Zn

II

-MFU-4

l

.

Figure 11.25 Framework structures of (a) [M

II

Cl

2

(bbta)] and (b) [M

II

M

III

(OH)Cl

2

(bbta)] (M = Mn, Co), as well as (c) the postoxidation strategy and CO

2

adsorption mechanisms of the two states.

Figure 11.26 Framework structure of [Zn

2

(Httb)

2

].

Figure 11.27 Coordination environment of the (a) octahedral and (b) tetrahedral zinc atoms, and (c) the simplified framework topology of MAF-34.

Chapter 12: Functional Linkers for Catalysis

Figure 12.1 Application of MOFs in catalysis: high cost catalysts for high value-added chemical synthesis.

Figure 12.2 Urea-functionalized NU-601 MOF.

Figure 12.3 Zr-MOF catalyst for Friedel–Crafts reaction.

Figure 12.4 Self-assembled amino acid-functionalized IRMOF-Pro.

Figure 12.5 Mo@UiO-67 as selective epoxidation catalyst.

Figure 12.6 Various substituted metalloporphyrins as MOF building blocks.

Figure 12.7 ZnPOR-1-catalyzed acyl transfer reaction.

Figure 12.8 Iron-porphyrin-based Zr-MOF as peroxidase mimic.

Figure 12.9 Ligand geometry-directed framework formation of salen-based MOF oxidation catalysts.

Figure 12.10 Postsynthetic organocatalyst grafting on Cr-MIL-101 open metal sites.

Figure 12.11 Postsynthetic hydrophobization of SIM catalyst.

Figure 12.12 Tailoring activity by dual postsynthetic functionalization of DMOF: basic hydrophobic balance.

Figure 12.13 Copper-functionalized MOF-253 as cross-coupling catalyst.

Figure 12.14 Variety of postsynthetic modification of IRMOF-3 with different metal complexes of Au [76], V [64a], and Mn [77] (from left to right) and their catalytic applications.

Figure 12.15 Postsynthetic grafting of Cu-based molecular catalyst inside Cr–MIL-101–NH

2

.

Figure 12.16 UMCM-1-AMpz and UMCM-1-AMsal as host matrix for Fe-, In-, and Cu-based catalysts.

Figure 12.17 Efficient Ni@MIL-101 catalyst through one-pot postsynthetic grafting inside Fe-MIL-101-NH

2

.

Figure 12.18 Zr-MOF derivatives as solid nitrogen-containing chelating ligand for Ir-based catalyst.

Figure 12.19 Zr-UiO-66 as host matrix for Fe-based hydrogenase-like photocatalyst.

Figure 12.20 Different pathways for the covalent postsynthetic metalation of UiO-67 framework [88, 89].

Figure 12.21 DNP-enhanced solid-state NMR as highly sensitive characterization technique for organo-functionalized frameworks (left: microwave radical irradiation inside MOF cavity to get enhanced NMR signal; right:

14

N NMR spectra obtained for proline-functionalized MIL-68 without isotopic enrichment after few hours).

Figure 12.22 Determination of sample homogeneity for multifunctional MOFs by PTIR technique. (a) PTIR is coupling atomic force microscopy (AFM) and IR techniques; (b) imaging of MIL-68 needles.

Figure 12.23 Partial shrinkage of UiO-67 framework due to the coordination-induced bending of bipy ligand.

Figure 12.24 HYSCORE-EPR technique to determine the coordination of copper molecular complex anchored inside MIL-68. (a) Continuous EPR spectrum and (b) HYSCORE mapping.

Chapter 13: Chiral Linker Systems

Figure 13.1 (a) d-Alanine (

1

) with three donor sites to metal ions (M), (b) coordination environment of Ni

2+

in Ni(d-ala)

2

-ZMOF [3], and (c) l-glutamic acid (

2

) with five donor sites to metal ions (M).

Figure 13.2 Amide bond formation by amine and carboxylic acid derivative, proline-functionalized chir-H

2

bpdc

3

, and aspartic acid-functionalized trigonal linker

4

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.3 Cyclization of cysteine

5

for the synthesis of thiazolidine-based linkers and thiazolidine linker

6

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.4 Condensation reaction for the synthesis of NDIs and NDI derivative

8

functionalized with alanine. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.5 Nucleophilic substitution of cyanuric chloride (

9

) and alanine-substituted triazine linker

10

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.6 Click reaction for combination of azides with alkynes and proline-functionalized triazine linker

11

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.7 Synthesis of Schiff bases or reduced Schiff bases, Schiff base linker

12

, and reduced Schiff base linker

13

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.8 Peptide-based linkers. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure Scheme 13.1 Synthesis of oxalyl retro-peptide

19

by reaction of oxalyl chloride (

17

) with valine (

18

). The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.9 (a) Retro-peptide linkers

20

with variable side groups (R), pillaring ligand H

2

mbpz

21

and resulting coordination unit with Cu(NO

3

)

2

(coordination unit with (I) methyl-functionalized linker or (II) isobutyl-functionalized linker). MOF structures with (b) methyl-functionalized linker, (c) isopropyl-functionalized linker, (d) phenyl-functionalized linker, and (e) isobutyl-functionalized linker [35]. The asterisk symbol (*) marks chiral tertiary carbon atom, and hydrogen atoms are omitted for clarity.

Figure 13.10 Examples of natural multivariate linkers from chiral pool, d-(+)-camphoric acid (

22

), tartaric acid

23

, and malic acid

24

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure Scheme 13.2 Introduction of Evans auxiliary

25

to H

2

bdc based on amino acid precursor synthesizing chir-H

2

bdc

26

. The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.11 Structure of

i

Pr-chir-UMCM-1: (a) view along the

c

-axis and (b) model of one micropore highlighting chiral bdc units (only one position at bdc is shown for disordered oxazolidinone groups). Hydrogen atoms are omitted for clarity.

Figure 13.12 Examples for chiral linkers

27–29

based on ether group functionalities.

Figure Scheme 13.3 Condensation reaction for synthesis of the salen derivative

32

.

Figure Scheme 13.4 Synthesis of salen-based linkers

34

: (a) linker synthesis with donor side groups and (b) linker synthesis with pyridine units in backbone. ((i) Synthesis of salen backbone with aldehyde precursor

33

and (ii) metal ion infiltration for direct MOF synthesis.) The asterisk symbol (*) marks chiral tertiary carbon atom.

Figure 13.13 (a) Illustration of axial chirality with two atom pairs arranged around a chiral axis and (b) (

R

)- and (

S

)-BINOL, highlighting chiral axis (red arrow) and mirror plane (gray line).

Figure Scheme 13.5 Synthetic possibilities for BINOL-derived chiral linkers (

37

,

39

,

41

,

43

, and

46)

based on brominated BINOL ether

36

.

Figure 13.14 Crystal structure of CMOF-4b: (a) viewing direction along crystallographic

a

-axis and (b) viewing direction along crystallographic

c

-axis [62]. Hydrogen atoms are omitted for clarity.

Figure 13.15 Phosphorylated BINOL derivatives

47–48

with different substitution pattern.

Figure Scheme 13.6 Linear coordinating BINOL derivatives

50–51

based on bromine- and chlorine-functionalized precursor

49

.

Figure 13.16 BINAP-, biquinoline-, and biphenyl-based linkers

52–54

for MOF synthesis.

Figure 13.17 Linkers

55–57

with planar and axial chirality.

Figure Scheme 13.7 Synoptic view on enantioselective separation approaches and interactions using chiral MOF systems. (GC, gas chromatography; LC, liquid chromatography; HPLC, high-performance liquid chromatography; CEC, capillary electrochromatography).

Figure 13.18 Chiral linkers (left in column) and substrates (right in column), which were applied in stereoselective HPLC separation with MOFs synthesized using the illustrated chiral linkers.

Chapter 14: Functional Linkers for Electron-Conducting MOFs

Figure 14.1 Common methods for measuring electrical conductivity. (a) Four-probe and (b) two-probe methods for powder samples and single crystals (dimensions

l

,

a

, and

d

are the voltage probe distance, the sample width, and thickness, respectively). (c) The four-point and (d) the van der Pauw methods for very thin samples.

Figure 14.2 The crystal structure of MOF-5 shown as ZnO

4

tetrahedra joined by benzene dicarboxylate linkers [9].

Figure 14.3 (a) Experimental configuration for measuring electrical conductivity of MOF single crystals and (b) the SEM image of MOF-5 crystal probed in SEM.

Figure 14.4 (a) Conceptual design of MOFs containing (–M–S–)

∞

chains obtained by replacing phenol groups in M

2

(DOBDC) with thiophenol groups. (b) Conductivity transients observed by FP-TRMC. (c) Photocurrent transients observed by TOF for methanol-exchanged and activated sample.

Figure 14.5 (a) The infinite helical Zn-carboxylate chains and (b) a side view of a helical TTF stack with a depiction of the shortest intermolecular S···S contact. (c) Conductivity transients observed by FP-TRMC upon and (d) photocurrent transients observed for 20–26 µm thick solid films of materials. (Reproduced from [13]. Copyright 2012, with permission from American Chemical Society). (e) Correlation between SS distance and electrical conductivity in M

2

(TTFTB).

Figure 14.6 (a) Coordination environment of Zn atoms in {[Zn

3

(DLlac)

2

(pybz)

2

]·2.5DMF}

n

. (b) Perspective views of the 3D open framework with 1D channel in {[Zn

3

(DLlac)

2

(pybz)

2

]·2.5DMF}

n

, the guest DMF molecules being shown in channels. (c) The completely desolvated framework {[Zn

3

(DLlac)

2

(pybz)

2

]}

n

. (d) Sketch of I

2

molecules diffusing in the channels of {[Zn

3

(DLlac)

2

(pybz)

2

]}

n

.

Figure 14.7 [Cu

3

(BTC)

2

(H

2

O)

3

]

n

viewed along the cell body diagonal [001].

Figure 14.8 Electronic transport characteristics of HKUST-1 thin film.

I–V

curves before (red) and after infiltration with TCNQ (green), F4-TCNQ (gold), or H4-TCNQ (purple).

Figure 14.9 Molecular structures of

N,N

′-dithiooxamido (dtoa) and 2,3-pyrazinedithiolate (pdt).

Figure 14.10 (a) Proton-coupled redox property in H

2

dtoaCu. (Reproduced from [20]. Copyright 2003, with permission from Elsevier). (b) Two-dimensional coordination polymer of catena-μ-

N,N′

-bis-(hydroxyethyl)dithiooxamidatocopper (II). Dibasic acid character of the ligand.

Figure 14.11 (a) Time decrease (%) of conductivity, at (1) 22 °C, (2) 50 °C, and (3) 78 °C and (b) effects of temperature on specific conductivities for both

σ

e

and

σ

H

(○:

σ

e

, •:

σ

H

).

Figure 14.12 (a) The schematic illustration of the reaction. (b) Crystal structure of Na[Cu

III

(pdt)

2

]·2H

2

O. View along the stacking axis

a

.

Figure 14.13 Electrical resistivity of Na[Ni(pdt)

2

]·2H

2

O.

Figure 14.14 (a) Crystal structure of Cu[Cu(pdt)

2

]. (b) Perspective view of the crystal structure of Cu[Cu(pdt)

2

]. (Reproduced from [28]. Copyright 2008, with permission from American Chemical Society). (c,d) Conductivity of Cu[Ni(pdt)

2

] film cast on Pt-interdigitated electrodes.

Figure 14.15 Schematic representation of MV MX, CDW for Pd and Pt complexes (a) and SDW for Ni (b).

Figure 14.16 Schematic of the fabrication of [Pt(en)(bpy)I]

4

(NO

3

)

8

·16H

2

O nanotube.

Figure 14.17 Possible electronic states in MMX chains.

Figure 14.18 Structure of a [Pt

2

(

dta

)

4

I]

n

(

dta

= dithioacetato) single fiber.

Figure 14.19 (a) Diamondoid geometry of [Rh

2

(acam)

4

(H

2

O)

2

]·6H

2

O. (b) Arrangement of [Rh

2

(acam)

4

] units and water molecules around an iodide atom.

Figure 14.20 Molecular structures of 1,2,3-triazoles, 1,2,4-triazoles, and tetrazole.

Figure 14.21 Illustration of the series of METs.

Figure 14.22 (a) Pyridine-2-thiolate (C

5

NH

4

S), (b) pyrimidine-2-thiol (C

4

N

2

H

3

S), (c) view of the lamellar structure in [Ni

2

(C

4

N

2

H

3

S)

4

]

n

, and (d) the structure of the basic unit [Ni

2

(C

4

N

2

H

3

S)

4

].

Figure 14.23 Molecular structures of catechol, benzenehexathiol (BHT), 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP), 2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride (HATP·6HCl), and 2,3,6,7,10,11-triphenylenehexathiol (HTT).

Figure 14.24 Space-filling drawings of the single-crystal structure of Co-CAT-1. (a) View of the Co-CAT-1 structure along the

c-

axis. (b) Extended layer of Co-CAT-1. (c) Layer formed by the trinuclear complexes Co

3

(HTTP)(H

2

O)

12

. (d) View of the two extended corrugated layers along the [110] direction.

Figure 14.25 View of the porous structure of Ni

3

(HITP)

2

.

Figure 14.26 Schematic illustration and chemical structure of monolayer nickel bis(dithiolene) complex nanosheet.

Figure 14.27 (a) Illustration of the chemical structure of the nickel bis(dithiolene) complex nanosheet. (b) Schematic illustration on redox control. (c) The SEM image for the van der Pauw measurement of ox-1.

Figure 14.28 (a) A schematic drawing of the honeycomb net of HTT-Pt, (b) a single net from a crystal structure model based on standard bonding geometries, and (c) the stacking of two neighboring sheets.

Figure 14.29 Chemical structure of TCNQ, TCNQ

•−

, and TCNQ

2−

.

Figure 14.30 The crystal structures of Cu(TCNQ) (a) phase I and (b) phase II; views of the two interpenetrating networks in (c) phase I and (d) phase II; and (e) plots of conductivity

σ

(S cm

−1

) versus temperature for bulk Cu(TCNQ) phases I and II.

Figure 14.31 A perspective view of the crystal structure along the short axis of Tl(TCNQ) (a) phase I and (c) phase II and side views of the crystal structures of (b) phase I and (d) phase II; (e) conductivity measurements performed on pressed pellets of phase I (

1

) and phase II (

2

) of Tl(TCNQ).

Figure 14.32 Semilogarithmic plots of the conductivity

σ

versus 1/

T

for samples.

Figure 14.33 (a) Packing diagram of Cd

2

(TCNQ)

3.5

(H

2

O)

2

; (b) temperature dependence of the electron conductivity (

σ

) of a single crystal of the compound. Inset: Arrhenius plot of the conductivity (the red line shows the linear fit of the data).

Figure 14.34 The 2D coordination network of Ru

2

II,II

/TCNQ.

Figure 14.35 Packing diagrams of [{Ru

2

(O

2

CCF

3

)

4

}

2

-(TCNQF

4

)]·

n

(solv) projected along (a) the

c

-axis and (b) the

b

-axis; (c) temperature dependence of the resistivity (

ρ

).

Figure 14.36 General crystal framework for PBAs (a) and schematic structure of Fe in PB (b).

Figure 14.37 Schematic crystal structures of PBA. (a) M

A

II

[M

B

III

(CN)

6

]

2/3

·

z

H

2

O and (b) A

I

M

A

II

[M

B

III

(CN)

6

].

Figure 14.38 (a) Diffuse reflectance spectra for Fe

4

[Fe(CN)

6

]

3

·14H

2

O, Fe

4

[Ru(CN)

6

]

3

·18H

2

O, and K

1.2

Ru

3.6

[Ru(CN)

6

]

3

·16H

2

O and (b) temperature dependence of the electrical conductivity of K

1.2

Ru

3.6

[Ru(CN)

6

]

3

·16H

2

O.

Chapter 15: Linkers with Optical Functionality

Figure 15.1 Energy level diagram (also known as a

Figure 15.2 A hierarchy of MOF structure using the parallel with the four levels of structure in proteins.