Edited byRolfGleiter, Henning Hopf

@WILEY-VCH

ModernCyclophane Chemistry

Contents

Preface XV

List of Contributors XVII

1 Cyclophynes LYoshito Tobe ond Motohiro Sonoda

1.1 Introduction 11.2 Orthocydophynes and Related Systems 21.2.L Planar Dehydrobenzoannulenes 3t.2.2 Nonplanar Orthocydophynes 1.3L.3 Metacydophynes and Related Systems 17t.4 Paracydophynes and 1,3,5-Bridged Cydophynes 281.5 Conduding Remarks 351.6 Ad<nowledgement 361.7 References 36

2 Hetera (Cyclo-)phanes 41Fritz Vögtle, Gregor Pawlitzki, and Uwe Hahn

2.t Introduction 4L2.!.1 Selection of Topics Presented 412.L2 Definitions 422.1.3 Why Conduct a Suwey on Heteraphanes? 492.2 Heteraphanes 512.2.1 Planar Chiral and Helical Chiral Phanes 512.2.t.1, Design of Phanes with Planar and Helical Chirality 512.2.1.2 Hetera [2.2]Metacydophanes 532.2.1.3 PlanarChiral[2.2]Metacyclophanes 552.2.t.4 Planar Chiral Hetera [n]Para- and Hetera [n]Metacydophanes 562.2.1.5 Dioxa [2.2]Phanes and Oxaza [2.2]Phanes 572.2.t.6 Enantiomer Separations 572.2.1.7 Strongly Helical Heteraphanes 582.2.2 Catenanes, Rotaxanes, and Knotanes of the Heteraphane Type 592.2.2.1 Template Synthesis of Rotaxanes Using Cydophane Wheels 59

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2.2.2.2 Higher Order fn]Rotaxanes via Non-ionic Template Effect 602.2.2.3 Combination of Anionic and Non-ionic Template 612.2.2.4 Molecular Knots and Similar Macrocydes of the Heteraphane

Tfpe 612.2.3 Further Heteraphanes, Metallaphanes and Supramolecular Phanes 622.3 Condusions 622.4 Acknowledgement 742.5 References 74

3 Highly Strained Cyclophanes 81nKasnl lsuJr

3.1 Introduction 813.2 [r,r]Metacydophanes 813.2.1 Synthesis 813.2.2 Strucrures and Physical Properties 833.2.3 Reactions of Strained [r]Metacydophanes 843.2.3.I Thermal and Photochemical Reactions 843.2.3.2 Addition Reactions 853.2.3.3 Reactions with Eleckophiles 863.2.3.4 Reactions with Nudeophiles 873.3 [n]Paracydophanes 893.3.1 Synthesis 903.3.2 Structures and Physical Properties 913.3.3 Reactions of Süained [n]Paracydophanes 923.3.3.1 Thermal and Photochemical Reactions 923.3.3.2 Reactions with Electrophiles 943.3.3.3 Diels-Alder and Other Reactions 943.3.3.4 Kinetic Stabilization of [4]Paracydophane Systems 953.4 Aromaticity of Bent Benzene Rings 963.5 Cyclophanes containing Polycydic Aromatic Rings:

(2,7)Pyrenophanes 963.6 [1.1]Paracyclophanes 983.6.1 Synthesis 993.6.2 Kinetic Stabilization of f1.1]Paracydophane Systems 1003.6.3 Stnrchrres and Physical Properties 1.003.7 References and Notes L02

4 Superphanes 105RoIf Gleiter and RoIf Roers

4.t Introduction 1054.2 [n2]Cydopropenonophanes 1064.2.1 Synthesis 1064.3 Superbridged Cydopropenyliophanes 1094.4 Ca-Superphanes 1094.4.1 Properties of Cydobutadieno Superphanes 11.5

Contents lvnI

4.4.2 Oxidative Demetallations 1164.5 C5-Superphanes 1.174.6 Superbridged Benzene Rings 1204.7 Concluding Remarks 1.264.8 Acknowledgement 1274.9 References 1.27

5 Carbon-Bridged Ferrocenophanes 1i1

Joon-Seo Park and T. Randall Lee5.1 Introduction 1315.2 Nomenclature 1325.3 Mononudear Carbon-Bridged Ferrocenophanes 1335.3.1 [1]Ferrocenophanes 1335.3.2 [2]Ferrocenophanes 1.345.3.3 [3]Ferrocenophanes 1365.3.4 [4]Ferrocenophanes 1405.3.5 [5]Ferrocenophanes 1445.3.6 [rn]Ferrocenophanes (nr>5) i.465.3.7 Multiply-BridgedMononudearFerrocenophanes

([nr.],Ferrocenophanes) 1475.4 Multinuclear Ferrocenophanes i.505.4.1. [0.0]Ferrocenophanes 1505.4.2 [1"]Ferrocenophanes L515.4.3 m']Ferrocenophanes 1535.5 Summary 1545.6 References 154

6 Endohedral Metal Complexes ofCyclophanes 159Rolf Gleitea Bemhard. J. Rausch, ond Rolf J. Schaller

6.1 Introduction 1596.2 Singly-Bridged Group IVB Metallocenes 1606.2.L Singly-Carbon-Bridged Group IVB Metallocenes 1606.2.2 Singly-Silicon-BridgedGrouplVBMetallocenes i.616.2.3 Singly-Boron- and Phosphorous-Bridged Group IVB Metallocenes 1626.3 Doubly-Bridged Group IVB Metallocenes 1636.3.1 Doubly-Carbon-Bridged Group IVB Metallocenes 1636.3.2 Doubly-Silicon-Bridged Group IVB Metallocenes 1656.3.3 Sbrrctural Features of Doubty-Bridged Group IVB Metallocenes 1666.4 Endohedral Group VIB and VIIIB Metal z-Complexes J.686.4.1, Bridged Bisfbenzene]chromium Complexes 1686.4.2 Bridged Metallocenophanes of Group VIIIB Metals 1206.5 Cavities as Hosts for Cations of Group IB, IIIA and IVA Metals 1766.5.1 Endohedral Silver Complexes with Cyclophanes 1766.5.2 Silver Complexes with z-prismands 1906.5.3 Group IIIA and IVA Complexes of Cydophanes 181

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6.5.4 Group IIIA Complexes with z-Prismands 1826.6 Conduding Remarks 1846.7 Achrowledgments 1846.8 References 184

7 lntramolecular Reactions in Cyclophanes 189Henning Hopf

7.1 Introduction 1897.2 Reactions between the Benzene Rings of Cydophanes L907.3 The Pseudo-gem Effec. 1987.4 Intramolecular Reaction between Functional Groups

in Cydophanes 2017.5 Condusions 2077.5 References 208

8 Reactive Intermediates from Cyclophanes 21,LWolfram Sander

8.1 Thermolysis of f2.2]Paraqdophanes 2118.2 Photolytical Cleavage of [2.2]Paracydophanes 2178.3 Cleavage of [2.2]Paracydophanes via Elecrron Transfer 2208.4 Cleavage of Cydophanes with Unsaturated Bridges 221.8.5 Cleavage of Cydophanes with Carbonyl Groups in the Bridge 2238.6 References 226

9 X-ray Crystal Structures of Poiphyrinophanes as Model Compounds forPhotoinduced Electron Transfer 229Hennann Imgartinger and Thomas Oeser

9.1 Introduction 2299.2 Porphyrin-Quinone Cyclophanes 2309.2.1 Double-BridgedPorphyrin-QuinoneCydophanes 2309.2.2 Single-BridgedPorphyrin-QuinoneCydophanes 2329.2.2.L Phenyl-SpaceredPorphyrin-Quinone Cydophanes 2329.2.2.2 Naphthalene-Spacered Porphyrin-QuinoneCydophanes 2359.3 Porphyrin-Aromatic-Ring Cydophanes 2389.3.L Single Bridge from Opposite meso-Positions 2389.3.1.1 Substituted Phenyl Rings as Cydophane Components 2389.3.1.2 Polycydic Aromatic Ring-Systems as Cydophane Components 2439.3.1.3 Aromatic Heterocycles as Cydophane Components 2459.3.2 Single Bridge from Opposite non-rneso-Posilons 2489.3.3 Capped Porphpins 2499.4 Porphyrinophanes with Fullerene Hosts 2539.5 Conduding Remarks 2549.6 References 255

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Ultraviolet Photoelectron Spectra of CyclophanesHeidi M. Muchall 259Introduction 259

[2.2]Pararydophane 263Modified Bridges in [2.2]Paracydophane 265Conjugating Substituents in [2.2]Paraqdophane 266Donor-Acceptor Cydophanes 268Heterocydophanes 270Miscellaneous Compounds 270

[6]Phanes with Higher Aromatic Systems 270Cydopropenophanes 271Metacydophanediynes 272References 273

UV'/Yis Spectra of Cyclophanes 275Paul RaderruacherIntroduction 275Characteristic Properties of Cydophanes with Implicationsfor their Electronic Spectra 275

[n]Cyclophanes 277

fm.n]ParacycJophanes 279

[1.1]Paracydophane 279

[2.2]Paracydophane 280

fm.nlPancydophanes 284Mdtibridged [2"]Cydophanes and Related Compounds 285

[nc.n]Arenophanes 288

[m.n]Naphthalenophanes 288

[n.n]Pyrenophanes 289FluorinatedCydophanes 290Heterorydophanes 290MultiJayeredCydophanes 297Donor-AcceptorCydophanes 298Donor-Acceptor Substituted fn.n]Paracydophanes 298

[n.zr.]Paracydophane Quinhydrones 300

fr..nlMetacyclophane Quinhydrones 303Oligooxa[rn.n]paracydophane Quinhydronesand Related Compounds 304Donor-Acceptor Substituted [n.n]Cydophanes with Extensivez-Electron Systems 305References 307

Electronic Circular Dichroism of Cyclophanes 311Stefan Gimme and Amold BahlmannIntroduction 3i.1Theoretical Methods 312

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12.3 Excited States of Model Compounds 31412.3.7 Boat-type Deformation in Benzene 31412.3.2 Interacting Benzene Fragments 31972.4 Theoretical and Experimental CD Spectra of Cydophanes 32312.4.I fn]Cydophanes 32312.4.t.1 9,12-Dimethyl4-oxafTlparacydophane 32372.4.1..2 [6]Paracydophane-8-carboxylicAcid 32412.4.2 [2.2]Paracydophanes 325L2.4.2.L [2.2]Paracydophane 325L2.4.2.2 4-Fluoro-f2.2lparacyclophane 3271,2.4.2.3 a-Methylf2.2]paracydophane 329t2.4.3 [2.2]Metacydophanes 331L2.4.3.I l-Thiaf2.2]metacydophane 33112.4.3.2 1-Thia-10-aza[2.2]metacydophane 332L2.4.4 Cyclophanes with Two Different Aromatic Rings i33t2.4.4.I 14,17-Dimethyl[2](1,3)azuleno[2]paracydophane 333I2.5 Condusions 33472.6 Adcrowledgement 33512.7 References 335

13 Fully Conjugated Beltenes (Belt-Like and Tubular Aromatics) 337Rainer Herges

13.1 Introduction 3371,3.2 Approaches Towards Fully-Conjugated Beltenes 34113.3 Belt-like Benzoannulenes (8) 34273.4 [0"]Paracydophanes 7 34413.5 Möbius Belts 35413.6 Conjugated Belts from Rrllerenes 35513"7 References 356

'14 Molecular Electrochemistry of Cyclophanes 359Bemd Speiser

14.1 Introduction 359t4.l.t EIecEon T?ansfer and Molecular Electrochemistry i59L4.1.2 Molecular Eleclrochemistry of Cydophanes 35914.1.3 Methods of Molecular Electrochemistry 36014.2 Molecular Electrochemistry of Hydrocarbon Cydophanes 361t4.3 Molecular Electroc-hemistry of Functionalized Cydophanes 363L4.3.1 Substituted Cydophanes 36314.3.2 Cydophanes vrith Non-metallic Heteroatoms as Ring Members 364I4.4 Molecular ElectrochemistryofOrganometallic Cydophane

Derivatives 367L+.4.1 A Possible Classification of Organometallic Cydophane

Derivatives 367t4.4.2 MetallocenophanesandMetallametallocenophanes 367

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74.4.3 Cydophanes as z-Complex Ligands 370t4.4.4 Cyclophanes as Supramolecular Components 374t4.5 Conclusions 37614.6 References 376

15 NMR Spectra of Cyclophanes 381Lud.ger Ernst and Kerstin Ibrom

15.1 Introduction and Scope 38115.2 [n]Phanes 38215.2.1 [n]Metacydophanes i8275.2.2 fzr]Paracydophanes 38575.2.3 Other [n]Phanes 38715.3 [2.2]Phanes 38975.4 [3.3]Phanes 39615.5 [nr..n]Phanes (m>2, n>2) 40015.6 [nr.,]Phanes 406t5.7 Oiher Phanes 40915.8 Condusion 41215.9 References 41.2

15 Strained Heteroatom-Bridged Metallocenophanes 415Ian Manners and, Uf Vogel

16.1 Introduction 41516.2 Synthesis and Structure 416L6.2.1 [l]Ferrocenophanes 416L5.2.1.1 Group 13 Bridged fl]Ferrocenophanes 41716.2.1..2 Group L4 Bridged fl]Ferrocenophanes 41.716.2.L.3 Group L5 Bridged [1]Ferrocenophanes 41916.2.7.4 Group 16 Bridged [l]Ferrocenophanes 41916.2.2 Other [l]Metallocenophanes 419t6.2.3 [2]Ferrocenophanes 42016.2.4 Other f2]Metallocenophanes 42216.3 Ring-Opening Polymerization of Strained Ferrocenophanes 42216.3^1 Stoichiometric Insertion and Ring-Opening Reactions 4221'6.3.2 Ring-Opening Polymerizations (ROP) 42316.3.2.1 Thermal ROP 42316.3.2.2 Living Anionic ROP of Silicon-Bridged [1]Ferrocenophanes 42416.3.2.3 Tkansition Metal-Catalyzed ROP of [L]Ferrocenophanes 4251'6.3.2.4 Other Initiation Methods for ROp 42616.4 Properties and Applications of Ring-Opened Polyferrocenes 4261,6.4.I Poffirrocenylsilanes 426L6.4.2 Other Poly:netallocenes via ROp 43016.5 References 431

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17 Cyclophanes as'Ibmplates in Stereoselective Synthesis 435Yaleio Rozenberg, Elena Sergeeva, and. Henning Hopf

77.L Introduction 43517.2 Chiral[2.2]Paracyclophanes: NomenclatureandStereochemical

Assignment 43517.3 The Resolution of Representative Mono- and Disubstituted

lL.2lParacycJophanes 43717.4 Monosubstituted l2.2lParacryclophanes as Chiral Inductors 4i7L7.5 Disubstituted [2.2]Paracydophanes as Chiral Inductors 440t7.5.1 Ortho-andsyn-Iatero-SttbstitutedDerivatives 44017.5.2 Pseud'o-ortho-Derivatives 44917.5.3 Pseudo-gem-Derivatives 45217.6 ChiralTemplatesfromSubstituted[2.2]Paracydophanes

as Building Blocks 45417.7 Stereoselective Reactions in the Side Chain of the Paracydophanyl

Moiety 45717.8 Conduding Remarks 458l7.9 References 459

18 Vapor-BasedPolymerizationofFunctionalized[2.2]Paracyclophanes:

. A Unique Approach towards Surface-Engineered Microenvironments 463Dois Klee, Norbert Werss, and Jörg Lahann

18.1 Introduction 463t8.2 SyrthesisofFunctionalizedf2.2lParacydophanes 46418.3 CVD Polymerization of Functionalized [2.2]Paracydophanes 46618.4 Immobilization of Bioactive Substances via Functionalized

Poly(p-xylylenes) 472L8.4.1, Introduction 472t8.4.2 Surfaces for Blood Contact 47518.4.3 Surfaces for Tissue Contact 47618.4.4 Surface Engineering of Microfluidic Devices 47818.5 Condusions 48118.6 References 482

19 From Cyclophanes to Molecular Machines 485Amar H. Flood., Yi Liu, and J. Froser Stoddart

19.1 Introduction 48519.1.1 Control over the Location and Motion of Moving Parts in Molecular

Machines 48519.2 The Creation of *re Tetracationic Cydophane 48619.3 Host-Guest Chemistry with the Tetracationic Cydophane 48819.3.1 Location Control: Host-Guest Chemistry 488I9.4 Catenane Chemistry with the Tetracationic Cydophane 49219.4.L Going for Gold - The Story of Olympiadane 49519.5 Rotaxane Chemistry with the Tetracationic Cyclophane 497

contents lxtttI

19.5.1 Location Control - Catenanes and Rotaxanes 499

19.6 Switchable Rotaxanes, Catenanes and Pseudorotaxanes 499

19.6.1 Controllable Molecular Shuttles 5001.9.6.2 Switchable Catenanes 50219.6.3 Switchable Rotaxanes 503t9.6.4 PhotochemicallySwitchablePseudorotaxanes 50319.6.5 Control of Motion 504tgJ Electronic Devices Containing Molecular Switches 50519.7.1 A [2]Catenane-Based Eiectronic Device 50619.7.2 Bistable [2]Rotaxane Electronic Devices 50819.7.3 Memory Devices 510t9.7.4 Miniaturization of the Crossbar 5L019.8 Mechanical Devices with Molecular Machines 51319.9 Condusions 51519.10 References 516

20 Molecular Recognition Studies with Cyclophane Receptorsin Aqueous Solutions 5L9Frangois Diederich

20.1, Introduction 51920.2 Complexation of Aromatic Solutes 52020.2.L Polar Effects in Cydophane Complexation 52020.2.2 Complexation of Polycydic Aromatic Hydrocarbons (PAHs)

in Water 52L20.2.3 The Combination of Apolar Binding and Ion Pairing Leads

to Very High Substrate Selectiviry 52i20.2.4 Solvent DependencyofCydophane-Arene Complexation

and the Nondassical Hydrophobic Effece Enthalpic Driving Forcesin Aqueous Solution 525

20.3 Steroid Recognition by Cyclophane Receptors 52720.3.1 The Search for Cyclophanes with Larger Preorganized Cavity-Binding

Sites 52720.3.2 Steroid Complexation by Cydophanes 9 and L0 52920.3.3 Double-decker Cydophanes for Effrcient Steroid Complexation:

Dissolution of Cholesterol in Water 53320.4 Catalpic Cydophanes 53620.5 Dendritically Encapsulated Cydophanes (Dendrophanes) 54120.6 Conclusions 54320.7 Acknowledgments 54320.8 References 544

Subject lndex 547