Macrocyclic and Supramolecular Chemistry

Dr. Reed M. Izatt, Charles E. Maw Professor of Chemistry (Emeritus), Brigham Young University, U.S.A. Reed M. Izatt received a BS degree in Chemistry from Utah State University (1951) and a PhD degree in Chemistry from Pennsylvania State University (1954). After post-doctoral work at Mellon Institute of Industrial Research, he embarked on an academic career at Brigham Young University retiring as Charles E. Maw Professor of Chemistry (1993). He is the author or co-author of over 550 publications. Reed has edited several books, contributed numerous chapters in books, written many journal and review articles and presented plenary, invited, and regular lectures at universities worldwide; regional, national, and international chemistry conferences; and government laboratories. Reed has been involved in research in macrocyclic chemistry since the late 1960s. Together with James Christensen, he organized the first Symposium on Macrocyclic Chemistry in Provo, Utah in 1977. This Symposium has thrived and was one of the major precursors of the present ISMSC.

List of Contributors xv

Preface xviii

Acknowledgements xx

1 The Izatt–Christensen Award in Macrocyclic and Supramolecular Chemistry: A 25-Year History (1991–2016) 1
Reed M. Izatt, Jerald S. Bradshaw, Steven R. Izatt, and Roger G. Harrison

1.1 Introduction 1

1.2 International Izatt–Christensen Award in Macrocyclic and Supramolecular Chemistry 2

1.3 International Symposium on Macrocyclic and Supramolecular Chemistry 4

1.4 Izatt–Christensen award sponsor: IBC Advanced Technologies, Inc. 6

1.5 Summary 7

References 8

2 Supramolecular Chemistry with DNA 10
Pongphak Chidchob and Hanadi Sleiman

2.1 Introduction 10

2.2 Motifs in structural DNA nanotechnology 10

2.3 Dynamic assembly and molecular recognition with DNA 13

2.4 Supramolecular assembly with hybrid DNA materials: increasing the letters of the alphabet 14

2.5 Conclusion 33

References 34

3 Anion, Cation and Ion-Pair Recognition by Macrocyclic and Interlocked Host Systems 38
Paul D. Beer and Matthew J. Langton

3.1 Introduction 38

3.2 Electrochemical molecular recognition 38

3.3 Anion recognition and sensing by macrocyclic and interlocked hosts 44

3.4 Halogen-bonding anion recognition 55

3.5 Ion-pair recognition 59

3.6 Metal-directed self-assembly 62

3.7 Conclusions 67

3.8 Acknowledgements 67

References 67

4 Perspectives in Molecular Tectonics 73
Mir Wais Hosseini

4.1 Preamble: dreams and pathway 73

4.2 Introduction 75

4.3 From tectons to networks 75

4.4 Summary and outlook 87

4.5 Acknowledgements 88

References 88

5 Three Tales of Supramolecular Analytical Chemistry 92
Margaret K. Meadows and Eric V. Anslyn

5.1 Introduction 92

5.2 Citrate sensing 93

5.3 Rapid analysis of enantiomeric excess 101

5.4 Differential sensing 109

5.5 Conclusion 123

References 123

6 Robust Host–Guest Chemistry of Cucurbit[n-uril: Fundamentals and Applications of the Synthetic Receptor Family 127
Kimoon Kim, Dinesh Shetty, and Kyeng Min Park

6.1 Personal pathway to the discovery of cucurbit[n-uril and early day developments 127

6.2 Structures and physical properties of CB[n- 129

6.3 General host–guest chemistry of CB[n- 129

6.4 High-affinity host–guest pairs 130

6.5 Functionalized CBs 133

6.6 Applications of high-affinity CB[6- complexes 134

6.7 Applications of high-affinity CB[7- complexes 137

6.8 Conclusions 140

6.9 Acknowledgements 141

References 141

7 Molecular Recognition in Biomimetic Receptors 146
Peter C. Knipe, Sam Thompson, and Andrew D. Hamilton

7.1 Molecular recognition in biological systems 146

7.2 Model systems to investigate fundamental forces 146

7.3 Recognition of more complex systems – into the realm of peptides 149

7.4 A general approach to peptide mimicry – targeting secondary structure 152

7.5 Super-secondary structures and beyond 156

7.6 Outlook 159

References 160

8 A Lifetime Walk in the Realm of Cyclam 165
Luigi Fabbrizzi

8.1 Synthesis and development of cyclam and related macrocycles 165

8.2 Macrocyclic effects and the importance of being 14-membered 170

8.3 Cyclam promotes the redox activity of the encircled metal ion 176

8.4 Scorpionands: cyclam derivatives with an aggressive tail, biting a chelated metal from the top 180

8.5 Azacyclams: cyclam-like macrocycles with built-in functionalization 187

8.6 Conclusion 193

8.7 Acknowledgements 195

References 196

9 Porosity in Metal–Organic Compounds 200
Alexander Schoedel and Omar M. Yaghi

9.1 Introduction 200

9.2 Werner complexes 201

9.3 Hofmann clathrates 201

9.4 Coordination polymers 204

9.5 Porosity in metal–organic frameworks 209

9.6 The discovery of MOF-5: the golden age of metal–organic frameworks 211

9.7 The Cambridge Structural Database – an essential tool for MOF chemists 214

9.8 Concluding remarks 215

9.9 Acknowledgement 215

References 215

10 Cyclodextrin-based Supramolecular Systems 220
Akira Harada

10.1 Introduction 220

10.2 Cyclodextrin-containing polymers 220

10.3 CD-organometallic complexes 222

10.4 Complex formation of cyclodextrin with polymers 223

10.5 Polymerization by CDs 225

10.6 Supramolecular polymers 228

10.7 Side-chain recognition by CDs 230

10.8 CD-based molecular machines 230

10.9 Macroscopic self-assembly through molecular recognition 233

10.10 Self-healing by molecular recognition 235

10.11 Stimuli-responsive polymers 236

10.12 Conclusion 238

References 238

11 Making the Tiniest Machines 241
David A. Leigh

11.1 Introduction 241

11.2 Property effects using molecular shuttles 245

11.3 Molecular motors and ratchet mechanisms 248

11.4 Small molecules that can “walk” along molecular tracks 254

11.5 Making molecules that make molecules 257

11.6 Outlook 257

11.7 Acknowledgements 259

References 259

12 Clipping an Angel’s Wings 261
Roeland J.M. Nolte, Alan E. Rowan, and Johannes A.A.W. Elemans

12.1 Introduction 261

12.2 Molecular clips 263

12.3 Molecular capsules 278

12.4 Outlook 282

12.5 Acknowledgements 282

References 283

13 From Lanthanide Shift Reagents to Molecular Knots: The Importance of Molecular and Mental Flexibility 288
Jeremy K.M. Sanders

13.1 Introduction: 1969–76 288

13.2 Metalloporphyrins 289

13.3 Macrocycles based on cholic acid 296

13.4 Designed donor–acceptor catenanes 297

13.5 Dynamic combinatorial chemistry 298

13.6 Conclusions 304

References 305

14 Texaphyrins: Life, Death, and Attempts at Resurrection 309
Jonathan L. Sessler

14.1 Introduction 309

14.2 Early days 309

14.3 Starting Pharmacyclics, Inc. 311

14.4 Early biological studies of texaphyrins 314

14.5 Clinical studies of texaphyrins at Pharmacyclics, Inc. 316

14.6 Changes in direction at Pharmacyclics, Inc. 316

14.7 Current research efforts involving texaphyrin 317

14.8 Texaphyrin-platinum conjugates 318

14.9 Acknowledgements 321

References 321

15 Macrocyclic Coordination Chemistry of Resorcin[4-arenes and Pyrogallol[4-arenes 325
Harshita Kumari, Carol A. Deakyne, and Jerry L. Atwood

15.1 Introduction 325

15.2 History of hydrogen-bonded pyrogallol[4-arene- and resorcin[4-arene-based nanocapsules 326

15.3 Metal-seamed pyrogallol[4-arene- and resorcin[4-arene-based complexes 327

15.4 Concluding remarks 342

References 342

16 Dynamic Control of Recognition Processes in Host–Guest Systems and Polymer–Polymer Interactions 346
Seiji Shinkai

16.1 Introduction 346

16.2 Dynamic control of crown ether functions by chemical and physical signals 347

16.3 Stereochemical studies of calix[n-arene derivatives 351

16.4 Ion and molecule recognition by functionalized calix[n-arenes and their application to super Na+-sensors and novel [60-fullerene isolation methods 351

16.5 Molecular design of novel sugar-sensing systems using boronic acid–diol macrocyclization 352

16.6 From molecular machines to allosteric effects 353

16.7 From allosteric effects to aggregation-induced emission (AIE) 354

16.8 Extension of cooperative actions to polymeric and biological systems 356

16.9 Summary 357

16.10 Acknowledgements 357

References 357

17 Cation Binders, Amphiphiles, and Membrane Active Transporters 360
George W. Gokel, Saeedeh Negin, Joseph W. Meisel, Mohit B. Patel, Michael R. Gokel, and Ryan Cantwell

17.1 Introduction 360

17.2 Conceptual development of lariat ethers for transport 361

17.3 Recognition of the ability of lariat ethers to form membranes 363

17.4 Use of lariat ethers to demonstrate cation–π interactions 365

17.5 Development of synthetic cation channels based on crown ethers 367

17.6 Development of synthetic anion channels based on amphiphilic peptides 370

17.7 Membrane active amphiphiles as biologically active and applicable compounds 371

17.8 Conclusion 373

References 373

18 Supramolecular Technology 377
David N. Reinhoudt

18.1 Introduction 377

18.2 Chemical sensing 378

18.3 Membrane transport 379

18.4 Nonlinear optical materials 380

18.5 Supramolecular technology for nanofabrication 380

References 382

19 Synthesis of Macrocyclic Complexes Using Metal Ion Templates 383
Daryle H. Busch

19.1 Introduction 383

19.2 Macrocycle synthesis 384

References 386

20 Serendipity 388
Paul R. McGonigal and J. Fraser Stoddart

20.1 Serendipity in scientific discovery 388

20.2 Donor–acceptor charge transfer interactions 390

20.3 Cyclodextrins (CDs) 400

20.4 Conclusions and outlook 410

References 411

21 Evolution of ZnII–Macrocyclic Polyamines to Biological Probes and Supramolecular Assembly 415
Eiichi Kimura, Tohru Koike, and Shin Aoki

21.1 Introduction 415

21.2 Zinc enzyme models from ZnII macrocyclic polyamine complexes 415

21.3 ZnII–cyclens for selective recognition of nucleobases (thymine and uracil) and manipulation of genes 427

21.4 New supramolecular assemblies with ZnII–cyclen 434

21.5 Acknowledgements 438

References 438

22 Contractile and Extensile Molecular Systems: Towards Molecular Muscles 444
Jean-Pierre Sauvage, Vincent Duplan, and Frédéric Niess

22.1 Preamble: the Izatt–Christensen award and Jean-Pierre Sauvage 444

22.2 Introduction 446

22.3 Interlocking ring compounds 447

22.4 Non-interlocking compounds 456

22.5 Conclusion 458

22.6 Acknowledgements 461

References 461

Index 465