Cryptophanes and Their Complexes—Present and Future

International audience1. Introduction 2. Syntheses of Cryptophanes 2.1. The “Direct (Two-Step) Method” 2.2. The “Template Method” 2.3. Coupling of CTVs 3. Syntheses of New Cryptophanes Using the Template Method 3.1. Deuterium Labeled Cryptophanes 3.2. Methylthio Containing Crytophanes 3.3. Amphipathic Cryptophanes 3.4. Syntheses of C2-Symmetrical Cryptophanes 4. Transformation and Functionalization of Cryptophanes 4.1. Water-Soluble Cryptophanes: Hexacarboxylic Acid Cryptophanes 4.2. Monofunctionalized Cryptophanes: Cryptophanol 4.3. Cryptophanes as Biosensors 4.4. Bis-cryptophanes 5. Structural Aspects and Characterization of Cryptophanes 5.1. Some Peculiarities in the Characterization of Cryptophane Hosts 5.2. Inverted and Imploded Cryptophanes 5.3. Molecular Structures of Cryptophane-A 1 and Related Ones 5.4. Some Aspects of Cryptophanes in the Crystalline State 6. Binding Properties of Cryptophanes 6.1. Complexation of Small Neutral Molecules 6.2. Complexation of Ammonium Guests 6.3. Complexation of Metal Cations 6.4. Complexation of Anion Guests 7. Dynamics of the Guest in the Cryptophane Cavity 7.1. Investigations by NMR Spectroscopy 7.2. Computational Investigations 7.3. Host−Guest Complexes in the Solid: Raman Microspectrometry 7.4. Studies in Mesophases 8. Chiral Discrimination 8.1. CHFClBr 8.2. CHFClI 9. Xenon in the Cryptophane Cavity 9.1. Xe@cryptophane Complexes 9.2. 129Xe NMR Spectroscopy of Xe@Cryptophane Complexes 9.3. Dynamics of Xenon Encapsulation 9.4. Laser-Polarized Xenon and Cryptophanes 9.4.1. Laser-Polarized Xenon in Cryptophane Complexes 9.4.2. Probing the Molecular Cavity of Cryptophane 9.4.3. “Functionalized” Xenon 10. Syntheses and Chiroptical Properties of Optically Pure Cryptophanes 10.1. Optical Resolution of CTVs and Cryptophanes 10.1.1. Optical Resolution Using Chiral HPLC 10.1.2. Resolution of CTVs 10.2. Syntheses of Optically Pure Cryptophanes 10.2.1. From Enantiopure CTVs 10.2.2. From Cryptophanol 10.3. Electronic Circular Dichroism (ECD) Spectra of Resolved Cryptophanes 10.3.1. ECD of CTVs 10.3.2. ECD of D3-Symmetrical Cryptophanes 10.3.3. ECD of C1-Symmetrical Cryptophanes 10.4. VCD of Cryptophane Hosts 11. Conclusion—The Future of Cryptophanes 12. Dedicatio