Preface ........................................................ xi
1 Introduction ................................................. 1
1.1 Simple Ring Compounds ................................... 1
1.2 Three-Dimensional Aliphatic Carbon Structures ........... 3
1.3 Annulenes ............................................... 5
1.4 Multi-Ring Aromatic Structures .......................... 9
1.5 Porpyrins and Phthalocanines ........................... 10
1.6 Conclusions ............................................ 13
References .................................................. 14
2 Cyclophanes ................................................. 16
2.1 Introduction ........................................... 16
2.2 Cyclophanes with One Aromatic System and Aliphatic
Chain .................................................. 16
2.2.1 Properties of the cyclophanes ................... 17
2.2.2 Chemistry of the cyclophanes .................... 18
2.2.3 Synthesis of the cyclophanes .................... 19
2.3 Cyclophanes with More than One Aromatic Ring ........... 20
2.4 Napthalenophanes and Other Aromatic Systems ............ 25
2.5 Cyclophanes Containing Heteroaromatic Systems .......... 28
2.6 Ferrocenophanes ........................................ 28
2.7 Conclusions ............................................ 30
Bibliography ................................................ 30
References .................................................. 30
3 Crown Ethers, Cryptands and Other Compounds ................. 34
3.1 Introduction ........................................... 34
3.2 Crown Ethers ........................................... 35
3.3 Simple Complexes with Crown Ethers ..................... 37
3.4 Azacrowns, Cyclens and Cyclams ......................... 42
3.5 Crowns Containing Other Heteroatoms .................... 50
3.6 Lariat and Bibracchial Crown Ethers .................... 50
3.7 Cryptands .............................................. 54
3.8 Spherands .............................................. 56
3.9 Combined and Multiple Systems .......................... 60
3.10 Applications of Crown Ethers and Related Compounds ..... 67
3.11 Conclusions ............................................ 70
Bibliography ................................................ 70
References .................................................. 70
4 Calixarenes ................................................. 77
4.1 Introduction ........................................... 77
4.2 History ................................................ 77
4.3 Structures of Calixarenes .............................. 80
4.4 Chemical Modification of Calixarenes ................... 82
4.4.1 Modification of the hydroxyls ................... 82
4.4.2 Replacement of the hydroxyls .................... 86
4.4.3 Reaction of the rings ........................... 88
4.4.4 Reactions of the bridging groups ................ 89
4.4.5 Modification of the upper rim ................... 90
4.5 Complexes with Calixarenes ............................. 95
4.6 Bis and Multicalixarenes ............................... 98
4.7 Oxacalixarenes, Azacalixarenes and Thiacalixarenes .... 104
4.8 Resorcinarenes: Synthesis and Structure ............... 107
4.9 Cavitands and Carcerands .............................. 113
4.10 Conclusions ........................................... 116
Bibliography ............................................... 116
References ................................................. 117
5 Heterocalixarenes and Calixnaphthalenes .................... 126
5.1 Introduction .......................................... 126
5.2 Calixnaphthalenes ..................................... 126
5.3 Tropolone-Based Macrocycles ........................... 133
5.4 Calixfurans ........................................... 134
5.5 Calixpyrroles ......................................... 138
5.5.1 Introduction ................................... 138
5.5.2 Chemical modification of the calixpyrroles ..... 146
5.5.3 Confused calixpyrroles ......................... 152
5.5.4 Substituted calixpyrroles ...................... 153
5.5.5 Strapped calixpyrroles ......................... 158
5.5.6 Modification of the pyrrole units .............. 160
5.5.7 Sensing and other applications of
calix[4]pyrroles ............................... 161
5.5.8 Calixpyrroles including nonpyrrole units ....... 163
5.6 Calixindoles, Calixpyridines and Calixthiophenes ...... 172
5.7 Conclusions ........................................... 180
Bibliography ............................................... 183
References ................................................. 183
6 Cyclodextrins .............................................. 190
6.1 Introduction .......................................... 190
6.2 Complex Formation by Cyclodextrins .................... 195
6.3 Cyclodextrins of Other Sizes .......................... 207
6.4 Modification Reactions of Cyclodextrins ............... 208
6.4.1 Modification of the 6-hydroxyls ................ 209
6.4.2 Modification of the 2- or 3-positions .......... 211
6.5 Selectivity of Cyclodextrins .......................... 217
6.6 Multiple Cyclodextrin Systems ......................... 219
6.6.1 Bis and multi-cyclodextrins .................... 219
6.7 Polymeric Cyclodextrins ............................... 229
6.7.1 Covalently linked cyclodextrin polymers ........ 229
6.7.2 Noncovalently linked cyclodextrin polymers ..... 231
6.8 Cyclodextrins Combined with Other Macrocyclic
Systems ............................................... 231
6.9 Therapeutic Uses of Cyclodextrins ..................... 235
6.10 Other Uses of Cyclodextrins ........................... 238
6.11 Conclusions ........................................... 243
Bibliography ............................................... 244
References ................................................. 244
7 Cyclotriveratylenes and Cryptophanes ....................... 255
7.1 Introduction .......................................... 255
7.2 Synthesis of Cyclotriveratrylenes ..................... 255
7.3 Modification of Cyclotriveratrylenes .................. 263
7.4 Synthesis of Optically Active Cyclotriveratrylenes .... 268
7.5 Modification of the Bridging Groups ................... 269
7.6 Modification of the Aromatic Rings with
Organometallic Groups ................................. 273
7.7 Selective Binding Applications of
Cyclotriveratrylenes .................................. 276
7.8 Analogues of CTV ...................................... 287
7.9 Synthesis and Structure of Cryptophanes ............... 289
7.10 Modification of Cryptophanes .......................... 299
7.11 Complexes with Cryptophanes ........................... 303
7.12 Cryptophane-Xenon Complexes ........................... 308
7.13 Other Uses of Cryptophanes ............................ 312
7.14 Hemicryptophanes ...................................... 313
7.15 Conclusions ........................................... 315
Bibliography ............................................... 316
References ................................................. 316
8 Cucurbiturils .............................................. 325
8.1 Introduction .......................................... 325
8.2 Complexation Behaviour of Simple Cucurbiturils ........ 328
8.2.1 Cucurbit[5]uril ................................ 328
8.2.2 Cucurbit[6]uril ................................ 331
8.2.3 Cucurbit[7]uril ................................ 339
8.2.4 Cucurbit[8]uril ................................ 346
8.2.5 Cucurbit[10]uril ............................... 351
8.3 Modification of Cucurbiturils ......................... 354
8.4 Uses of Cucurbiturils ................................. 361
8.5 Hemicucurbiturils ..................................... 366
8.6 Conclusions ........................................... 368
Bibliography ............................................... 368
References ................................................. 368
9 Rotaxanes and Catenanes .................................... 381
9.1 Introduction .......................................... 381
9.2 Rotaxanes ............................................. 382
9.2.1 Synthesis using statistical methods ............ 382
9.2.2 Rotaxanes containing cyclodextrins,
cucurbiturils and calixarenes .................. 383
9.2.3 Rotaxanes based on тт -electron interactions ... 388
9.2.4 Other synthetic methods for rotaxane
synthesis ...................................... 392
9.2.5 Rotaxanes as molecular machines ................ 409
9.2.6 Thin films of rotaxanes ........................ 421
9.2.7 Polyrotaxanes .................................. 427
9.3 Catenanes ............................................. 430
9.3.1 Synthesis using statistical and directed
methods ........................................ 431
9.3.2 Catenates and catenanes via metal templates .... 432
9.3.3 Catenanes based on тт-electron interactions .... 450
9.3.4 Catenanes based on amide hydrogen-bonding
interactions ................................... 474
9.3.5 Catenanes containing other macrocyclic units ... 479
9.3.6 Switchable catenanes ........................... 485
9.3.7 Catenanes on surfaces .......................... 493
9.3.8 Polycatenanes and catenated polymers ........... 496
9.3.9 Natural catenanes .............................. 501
9.4 Conclusions ........................................... 504
Bibliography ............................................... 504
References ................................................. 505
10 Other Supramolecular Systems, Molecular Motors, Machines
and Nanotechnological Applications ......................... 518
10.1 Introduction .......................................... 518
10.2 Other Molecular Systems ............................... 518
10.2.1 Aromatic and cyclacene compounds ............... 518
10.2.2 Other cavitands ................................ 520
10.2.3 Pretzelanes, bonnanes and [1]rotaxanes ......... 525
10.2.4 Trefoil knots .................................. 526
10.2.5 Solomon links and Borromean rings .............. 539
10.2.6 Other systems .................................. 546
10.3 Molecular Devices, Motors and Machines ................ 549
10.3.1 Molecular and supramolecular switches .......... 550
10.3.2 Molecular motion ............................... 555
10.3.3 Light harvesting ............................... 565
10.3.4 Ion channels ................................... 566
10.3.5 Other uses of interlinked systems .............. 567
10.4 Conclusions ........................................... 567
Bibliography ............................................... 570
References ................................................. 570
Index ......................................................... 576
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