Calixarenes -- Contents -- Chapter 1 From Resinous Tar to Molecular Baskets -- 1.1 The Resinous Tar -- 1.2 Glistening Crystals: The Zinke Products -- 1.3 More Crystals: The Niederl Products -- 1.4 Cyclic Tetramers: Proofs of Structure -- 1.5 The Petrolite Chapter -- 1.6 Cyclic Tetramers and the Quest for Enzyme Mimics -- 1.7 Unraveling the Literature -- 1.8 Nomenclature and Representation of the Calixarenes -- Chapter 2 Making the Baskets: Synthesis of Calixarenes -- 2.1 One-step, Base-induced Synthesis of Phenol-derived Calixarenes -- 2.1.1 Synthesis of p-tert-Butylcalixarenes -- 2.1.2 Synthesis of Other p-Substituted Calixarenes -- 2.2 One-step, Acid-catalyzed Synthesis of Calixarenes -- 2.2.1 Phenol-derived Calixarenes -- 2.2.2 Resorcinol-derived Calixarenes -- 2.3 Multi-step Synthesis of Calixarenes -- 2.3.1 Non-convergent Stepwise Syntheses -- 2.3.2 Convergent Stepwise Syntheses (Fragment Condensation Procedure) -- 2.4 Synthesis of Calixarene-related Compounds -- 2.4.1 Norcalixarenes and Homocalixarenes -- 2.4.2 Oxacalixarenes, Azacalixarenes and Thiacalixarenes -- 2.4.3 Homooxacalixarenes and Homoazacalixarenes -- 2.4.4 Heterocalixarenes -- 2.5 Mechanism of Calixarene-forming Reactions -- 2.5.1 Mechanism of the Base-induced Reaction -- 2.5.2 Mechanism of the Acid-catalyzed Reaction -- 2.6 Concluding Remarks -- Chapter 3 Proving the Baskets: The Characterization and Properties of Calixarenes -- 3.1 Separation and Purification of Calixarenes -- 3.2 X-Ray Crystallography: The Ultimate Proof of Structure -- 3.3 Physical Properties of Calixarenes -- 3.3.1 Melting Points -- 3.3.2 Solubilities -- 3.3.3 pKa Values -- 3.4 Dipole Moments of Calixarenes -- 3.5 Spectral Properties of Calixarenes -- 3.5.1 Infrared Spectra -- 3.5.2 Ultraviolet Spectra -- 3.5.3 NMR Spectra -- 3.5.4 Mass Spectra -- 3.6 Concluding Remarks.

Chapter 4 Shaping the Baskets: Conformations of Calixarenes -- 4.1 Conformational Representation and Nomenclature -- 4.2 Computational Studies of Calixarene Conformations -- 4.3 Conformations of Calixarenes in the Solid State -- 4.3.1 Calix[4]arenes -- 4.3.2 Calix[5]arenes -- 4.3.3 Calix[6]arenes -- 4.3.4 Calix[7]arenes -- 4.3.5 Calix[8]arenes -- 4.3.6 Large Calixarenes -- 4.4 Conformations of Flexible Calixarenes in Solution -- 4.4.1 Conformational Mobility of Calix[n]arenes -- 4.4.1.1 Conformations of Calix[4]arenes -- 4.4.1.2 Conformational Mobility of Calixarenes Larger than Calix[4]arenes -- 4.4.1.3 Conformational Mobility of Oxacalixarenes and Azacalixarenes -- 4.4.1.4 Conformational Mobility of Calixresorcarenes and C-Substituted Calixarenes -- 4.4.1.5 Conformational Mobility of Thiacalixarenes -- 4.4.1.6 Conformational Mobility of Calixarene Ethers, Deoxycalixarenes, Calixquinones and Calixarenethiols -- 4.4.2 Pathways for Cone-cone Interconversion of Calix[4]arenes -- 4.5 Conformationally Immobile Calixarenes -- 4.5.1 Minimum Structural Requirements for Conformational Immobility of Unbridged Calixarene Ethers and Esters -- 4.5.1.1 Identification of Fixed Conformers -- 4.5.1.2 Fully Etherified and Esterified Calixarenes -- 4.5.1.3 Partially Etherified and Esterified Calixarenes -- 4.5.1.4 Meta-substituted Calixarenes -- 4.5.2 Conformational Immobilization via Bridging -- 4.5.3 Conformational Freezing via Oxygen-Metal Bridges -- 4.6 Factors Governing the Conformational Outcome of Derivatization -- 4.6.1 O-Tetrasubstitution of Calix[4]arenes -- 4.6.2 Mono-, Di- and Tri-O-substitution of Calix[4]arenes -- 4.6.3 O-Substitution of Calix[5]arenes and Calix[6]arenes -- 4.6.4 Calixarene Oxyanions -- 4.6.4.1 Calix[4]arene Oxyanions -- 4.6.4.2 Calix[6]arene Oxyanions -- 4.7 Chiral Calixarenes -- 4.8 Concluding Remarks.

Chapter 5 Embroidering the Baskets: Introduction of Functional Groups -- 5.1 Functionalization Involving the OH Groups -- 5.1.1 Esterification -- 5.1.2 Etherification -- 5.1.2.1 With Simple Alkyl Halides -- 5.1.2.2 With Functionalized Alkylating Agents -- 5.1.3 Endo Rim-bridged Calixarenes -- 5.1.4 Replacement of OH with H, N and S -- 5.2 Modifying the Exo Rim of Calixarenes -- 5.2.1 General Overview -- 5.2.2 Halogenation, Nitration, Sulfonation and Diazonium Coupling Routes -- 5.2.3 Alkylation (Including Chloromethylation) Route -- 5.2.4 Acylation and Aroylation Routes -- 5.2.5 Arylation Reactions -- 5.2.6 Aminomethylation: The p-Quinonemethide Route -- 5.2.7 p-Claisen Rearrangement Route -- 5.3 Functionalization of the Methylene Bridges -- 5.4 Exo Rim-Bridged Calixarenes -- 5.5 Oxidation of Calixarenes -- 5.5.1 Calixquinones -- 5.5.2 Spirodienones -- 5.6 Reduction of Calixarenes -- 5.7 Selective Functionalization -- 5.8 Concluding Remarks -- Chapter 6 Combining the Baskets: Multi-Calixarenes -- 6.1 Calixarenes Intermolecularly Bridged by Covalent Bonding -- 6.1.1 Bridging via the Endo Rims -- 6.1.2 Bridging via the Exo Rims -- 6.1.3 Multi-Calixarenes and Calixarene Dendrimers -- 6.2 Calixarenes Intermolecularly Bridged by Non-covalent Bonding -- 6.2.1 Dimeric Assemblies of Calixarenes -- 6.2.2 Catenanes and Rotaxanes -- 6.2.3 Oligomeric and Polymeric Assemblies of Calixarenes -- 6.2.4 Calixarenes in Monolayers and Interfaces -- 6.3 Calixarene Polymers -- 6.4 Concluding Remarks -- Chapter 7 Filling the Baskets: Complex Formation with Calixarenes -- 7.1 Solid State Complexes -- 7.2 Solution State Complexes of Metal Cations with Endo Rim-substituted Calixarenes -- 7.2.1 Complexation with Parent Calixarenes -- 7.2.2 Complexation with Endo Rim-substituted Calixarenes -- 7.2.2.1 Endo Rim Ethers -- 7.2.2.2 Endo Rim Esters -- 7.2.2.3 Endo Rim Ketones.

7.2.2.4 Endo Rim Amides -- 7.2.2.5 Endo Rim Carboxylic Acids -- 7.2.2.6 Endo Rim Phosphorus- and Sulfur-containing Groups -- 7.2.2.7 Nitrogen-containing Chelating Groups on the Endo Rim -- 7.2.3 Calixcrowns -- 7.2.4 Calixspherands -- 7.3 Solution State Complexes of Metal Cations with Exo Rim-substituted Calixarenes -- 7.4 Anion Complexes with Calixarenes -- 7.5 Salt Complexes with Calixarenes -- 7.6 Solution State Complexes of Molecules with Calixarenes -- 7.6.1 Complexes with Molecular Cations -- 7.6.2 Complexes with Neutral Molecules -- 7.6.2.1 Complexes in Aqueous Solution -- 7.6.2.2 Complexes in Non-aqueous Solution -- 7.7 Gas Phase Complexes -- 7.8 Theoretical Calculations -- 7.9 Templation -- 7.9.1 Templation in Calixarene Synthesis -- 7.9.2 Calixarenes as Templates -- 7.9.3 Templation in Conformational Phenomena -- 7.9.4 Allosteric Effects -- 7.10 Concluding Remarks -- Chapter 8 Using the Baskets: Calixarenes in Action -- 8.1 Calixarenes for Separations -- 8.1.1 Separations of Ions -- 8.1.2 Separations of Molecules -- 8.2 Calixarenes as Sensors -- 8.2.1 Ion- and Molecule-selective Electrodes -- 8.2.2 Field Effect Transistors -- 8.2.3 Chromogenic and Fluorescent Sensors -- 8.2.4 Nonlinear Optical Compounds -- 8.2.5 Other Sensors -- 8.3 Calixarenes as Catalysts -- 8.3.1 Biomimetic Catalysts -- 8.3.2 Non-biomimetic Catalysts -- 8.4 Calixarenes as Biomimetic and Physiological Compounds -- 8.5 Miscellaneous Applications -- 8.6 Patent Literature -- 8.7 Concluding Remarks -- Appendices -- Author Index -- Subject Index.