PKU CCME OPSS Shape-Persistent Macrocycles: From Molecules to Materials Jin-Liang Wang Supervisor: Jian Pei 2005. 12. 9 Outline Introduction Properties of the Shape-Persistent Macrocycles Synthetic Strategies to Shape-Persistent Macrocycles Advances in Shape-Persistent Macrocycles Höger Baüerle Mayor Moore Other groups Conclusion and Outlook
Introduction Crown Ether Conjugated Polymer Rigid ring Flexible side groups Shape-Persistent Macrocycles Introduction The side group orientation determines the properties of the macrocycles
Properties of the Shape-Persistent Macrocycles 1. Aromatic corner pieces interrupt the conjugation. 2. Solubility dramatically reduce. 3. High melting points. Synthetic Strategies to Shape-Persistent Macrocycles Chem.Commun. 2003, 807-818.
Synthetic Strategies to Shape-Persistent Macrocycles One-step cyclization High-dilution conditions!! The yields too low!! Difficult to purify!! H. A. Staab et al. Synthesis, 1974, 424 Synthetic Strategies to Shape-Persistent Macrocycles Intramolecular Cyclization Moderately high yield (ca. 60-80%) Control the size and functional group. Time-consuming on the precursor J. S. Moore, et al. Angew. Chem. Int. Ed. Engl., 1992, 31, 922.
Synthetic Strategies to Shape-Persistent Macrocycles Bimolecular Coupling Cyclization Pseudo-high-dilution conditions (< mm) The procedure more time-efficient. The strategy can applicable to a verity of coulping reactions Low yields than intramolecular coulping S. Höger, et al. Angew. Chem. Int. Ed. Engl., 1995, 34, 2713. Synthetic Strategies to Shape-Persistent Macrocycles Using non-covalent templates Sanders, et al. J. Am. Chem. Soc., 1995, 117, 6611.
Synthetic Strategies to Shape-Persistent Macrocycles Covalent Templated Cyclization The size can be controlled by the template. Good yield! Needed to attach and cleave the template. Höger, S. et al, J. Org. Chem. 1997, 62, 4556. Outline Introduction Properties of the Shape-Persistent Macrocycles Synthetic Strategies to Shape-Persistent Macrocycles Advances in Shape-Persistent Macrocycles Höger Baüerle Mayor Moore Other groups Conclusion and Outlook
Advances in Shape-Persistent Macrocycles Synthetic Strategies to Höger s Macrocycles Höger, S. et al, J. Am. Chem. Soc. 2001, 123, 5651-5659.
Synthetic Strategies to Höger s Macrocycles Extraannular Polyalkyl Substituents Höger, S. et al, J. Am. Chem. Soc. 2001, 123, 5651-5659. Two-Dimensional Organization of Höger s Macrocycles Monolayer of 1c adsorbed on graphite. STM image. 90 nm X 90 nm. Höger, S. et al, J. Am. Chem. Soc. 2001, 123, 5651-5659.
Two-Dimensional Organization of Höger s Macrocycles Monolayer of 1c adsorbed on graphite. high-resolution STM image. Höger, S. et al, J. Am. Chem. Soc. 2001, 123, 5651-5659. Discotic Liquid Crystals of Höger s Macrocycles Discotic Liquid Crystals Shape-Persistent Macrocycles J. Am. Chem. Soc. 2005, 127, 16233-16237. Chem. Eur. J. 2004, 10, 1320-1329. 9
Discotic Liquid Crystals of Höger s Macrocycles Texture of macrocycles at 200 o C Structure of macrocycles in the crystal Shape-Persistent Macrocycles Inverted Liquid Crystals Chem. Eur. J. 2004, 10, 1320-1329. Discotic Liquid Crystals of Höger s Macrocycles Structure of macrocycles in the crystal Texture of macrocycles at 150 o C Chem. Eur. J. 2004, 10, 1320-1329.
Functionalized Nanopatterned Surfaces Langmuir 2004, 20, 2781-2784. Functionalized Nanopatterned Surfaces STM Images on Au Langmuir 2004, 20, 2781-2784.
Coil-Ring-Coil Block Copolymers S. Höger, et al. Angew. Chem. Int. Ed.. 2001, 40, 3138. Supramolecular Hollow Cylindrical Brushes Nonspecific Interactions S. Höger, et al. Angew. Chem. Int. Ed.. 2001, 40, 3138.
Baüerle The First Fully Conjugated Macrocyclic Oligothiophene Angew. Chem. Int. Ed. 2000, 39, 3481-3486. Synthetic Strategies to Baüerle s Macrocycles Angew. Chem. Int. Ed. 2000, 39, 3481-3486.
Synthetic Strategies to Baüerle s Macrocycles Angew. Chem. Int. Ed. 2000, 39, 3481-3486. Synthetic Strategies to Baüerle s Macrocycles Angew. Chem. Int. Ed. 2000, 39, 3481-3486.
Synthetic Strategies to Baüerle s Macrocycles Angew. Chem. Int. Ed. 2000, 39, 3481-3486. Two-Dimensional Organization of Baüerle s Macrocycles Monolayer of 1 adsorbed on graphite. STM image (60nm) Angew. Chem. Int. Ed. 2000, 39, 3481-3486.
Two-Dimensional Organization of Baüerle s Macrocycles Monolayer adsorbed on graphite. STM image (28nm) Angew. Chem. Int. Ed. 2000, 39, 3481-3486. Mayor Angew. Chem. Int. Ed. 2003, 42, 3176-3179.
Synthetic Strategies to Mayor s Macrocycles Angew. Chem. Int. Ed. 2003, 42, 3176-3179. Uv/vis Spectra and MS of Mayor s Macrocycles Angew. Chem. Int. Ed. 2003, 42, 3176-3179.
Moore Chem.Commun. 2003, 807-818. Synthetic Strategies to Moore s Macrocycles J. Am. Chem. Soc. 1994, 116, 4227-4239
Aggregation of Moore s Macrocycles J. Am. Chem. Soc. 1994, 116, 4227-4239 Aggregation of Moore s Macrocycles Chem.Commun. 2003, 807-818.
New Synthetic Strategies to Moore s Macrocycles Alkyne Metathesis J. Am. Chem. Soc. 2004, 126, 12796-12796 New Synthetic Strategies to Moore s Macrocycles J. Am. Chem. Soc. 2004, 126, 12796-12796
Other Groups Shape-Persistent Macrocycles Heterodimer Association Tobe, et al. Org.Lett., 2000, 2, 3265-3268. Other Groups Shape-Persistent Macrocycles Self-aggregation Containing Heliene Yamaguchi. et al. Org.Lett., 2001, 3, 1097-1099.
Other Groups Shape-Persistent Macrocycles Ion-Induced Tubular Assembly Angew. Chem. Int. Ed. 2003, 42, 5307-5310. Other Groups Shape-Persistent Macrocycles Angew. Chem. Int. Ed. 2003, 42, 5307-5310.
Conclusion and Outlook 30 years before. Available in high yield even with small molecule. Conclusion and Outlook A modular building blocks for variety structures. such as ion channels, liquid crystalline materials.
Conclusion and Outlook Shape-Persistent Macrocycles Rigid Crown Ether Host-guest Chemistry Supramolecular Assemblies Catalytic Nanomaterials 2D 3D Metal Sensors Acknowledgement Prof. Pei Our Group Members All Professors & Ph.D Students
Acknowledgement