Important Announcements
Welcome to the course
Class schedule: Wednesdays, 15h30-17h00 in D3-2029
Course syllabus
Course objectives - To become familiar with supramolecular and macromolecular chemistry. To learn concepts of molecular recognition, self-assembly and macrocyclisation strategies involved in the fabrication of molecular and supramolecular materials.
Course syllabus -
The following subjects may be covered in this course: general concepts in macromolecular & supramolecular chemistry; the incorporation and exploitation of molecular recognition and autoassembly in medicine, computations, materials chemistry and green chemistry; control of topology during the synthesis of molecular knots and catenanes; supramolecular catalysis and photochemistry; macrocyclization strategies; the synthesis of bioorganic, organic and organometallic molecules.
Important dates:
Presentation of subject - abstract : week of May 24 (not more than 500 words)
Presentation of subject : week of June 28 (presentation of 45 minutes)
Research proposal : week of July 12
Presentation of research proposal : week of July 26 (presentation of 20 minutes + 10 minutes for questions)
Course Notes and Slides
Background Information
Non-Covalent Interactions
Classification
Charge-charge attraction/repulsion, charge-dipole, dipole-dipole interactions, hydrogen bonds, pi-stacking, C-H-pi, cation-pi interactions, pi-donor-pi-acceptor interactions, Van-der-Waals forces, hydrophobic effect.
Selected References
G.R. Desiraju, Acc. Chem. Res., 2002, 35, 565 |
Basic Principles in Supramolecular Chemistry
Concepts
Lock-and-key principle, induced fit, preorganisation, self-assembly versus self-organization, template effects, cooperativity, multivalency.
Selected References
G.F. Swiegers; T.J. Malefetse, Chem. Rev., 2000, 100, 3485 |
D.S. Lawrence; T. Jiang; M. Levett, Chem. Rev., 1995, 95, 2229 |
S.H. Gellman, Chem. Rev., 1997, 97, 1231 |
Molecular Recognition & Host-Guest Chemistry
Methods for the investigation of dynamically bound species: e.g., caffein receptor and its examination by NMR, IR, UV/VIS spectroscopies, mass spectrometry and crystallography.
Selected References
M.M. Con; J. Rebek Jr., Chem. Rev., 1997, 97, 1647 |
Chelate Effects & Preorganization
Understanding how to overcome entropically disfavoured reactions.
Selected References
C.J. Pedersen, J. Am. Chem. Soc., 1967, 89, 7017 |
J.M. Lehn, Angew. Chem. Int. Ed., 1988, 27, 89 |
D.J. Cram, Angew. Chem. Int. Ed., 1988, 27, 1009 |
Self-Assembly & Self-organization
Self-assembly and self-organization belong to the area of "emergent properties", i.e. a small set of well-defined rules plus simple building blocks make much more complex patterns evolve which are often almost unpredictable. New properties emerge that none of the building blocks have. For a very simple implementation with intriguing consequences, take a look at Conway's Game of Life (also see the related Wikipedia pages).
Selected References
M. Albrecht, Chem. Rev., 2001, 101, 3457 |
A-M Stadler, Eur. J. Inorg. Chem., 2009, 4751 |
Cooperativity & Multivalency
Cooperativity and multivalency are phenomena arising in molecular recognition at hosts with more than one binding site.
Selected References
Template Effects
A chemical template organizes reaction partners and thus allows the chemist to control their reactivity to achieve the formation of a desired product.
Selected References
M.M. Conn; J. Rebek Jr., Chem. Rev., 1997, 97, 1647 |
C.O. Dietrich-Buchecker; J.P. Sauvage, Chem. Rev., 1987, 87, 795 |
Self-Replication & Supramolecular Catalysis
Understanding the control of local concentration effects, the control of reactivity of functional groups.
Selected References
L. Kovbasyuk; R. Krämer, Chem. Rev., 2004, 104, 3161 |
D. Fiedler; D.H. Leung; R.G. Bergman; K.N. Raymond, Acc. Chem. Rev., 2005, 38, 349 |
J. Rebek Jr., Acc. Chem. Rev., 2009, 42, 1660 |
Molecular Devices and Machines: Implementing Function
Understanding how to impart functionality at the nanometer scale: molecular devices, logic gates, molecular motors
Selected References
E.R. Kay; D.A. Leigh; F. Zerbetto, Angew. Chem. Int. Ed., 2007, 46, 72 |
V. Balzani; A. Credi; F.M. Raymo; J.F. Stoddart, Angew. Chem. Int. Ed., 2000, 3348 |
For links to the animations see:
Kenneth Holmes, MPI Heidelberg |
Wolfgang Junge, Universität Osnabrück |
Hong Wang & Georg Oster, UC Berkeley/USA |
Katsuhiko Kinosita, Jr., Waseda University/Japan |
Case Examples in Detail
Architectures Based on Non-Covalent Bonds
Molecular Recognition, Container Molecules, Molecular Capsules and Cavitands
Selected References
Topologically Non-Trivial Molecules and Templated Synthesis
Crown Ethers, Catenanes, Rotaxanes, Molecular Knots
Selected References
Self-Assembly and Self-Organization: Creating Complexity from Simple Building Blocks
Helicates, Grids, Weaves, Metal-Organic Assemblies
Selected References
Catenanes, Rotaxanes as switches, Molecular shuttles, Light-driven machines, Logic gates
Selected References
Fluorescence Resonant Energy Transfer - FRET
Basic principles of FRET, what questions can be answered? Determination of binding
constants, Determination of distances, Artificial light-harvesting complexes
Selected References
Origin of Life: Self-Replication and Autocatalysis?
DNA replication, RNA world, Self-replication of oligonucleotides, Peptides and
organic minimal replicators, Kinetic analysis: square-root-law, Prion protein:
self-replication of conformations?
Selected References
E.A. Wintner, M.M. Conn, J. Rebek, Jr., Acc. Chem. Res. 1994, 27, 198 | |
L.E. Orgel, Nature 1992, 358, 203 | |
D.H. Lee, J.R. Granja, J.A. Martinez, K. Severin, M.R. Ghadiri, Nature 1993, 382, 525 |