Learning outcomes of the course unit
To gain the basic knowledge for the understanding and experimental setup of research studies aimed at the synthesis of new molecular receptors for the development of “devices” which exploit noncovalent interactions.
To fruitfully follow the course it is fundamental to have a solid knowledge of General Chemistry, Physical Chemistry and Organic Chemistry.
Course contents summary
Introduction to Supramolecular Chemistry. Molecular recognition. Intermolecular forces. Methods for the determination of the stoicheiometries of the complexes and of the complexation constants via different techniques (NMR, UV-vis, fluorescence, calorimetry, potentiometry,...). Extraction percentage and distribution coefficients.
Methodologies for the synthesis of macrocyclic compounds (crown, aza-crown, calixarenes, resorcarenes, cyclodextrins). Synthestic modifications of the macrocycles.
Cation complexation with crown-ethers, cryptands, spherands and ciclophanes: synthetic methodologies and complexation studies. Applications in the field of imaging (MRI, luminescent probes , radiolabelling), of radiotherapeutics, of metal detoxification and of the treatment of radioactive and heavy metals waste.
Neutral molecules complexation with crown-ethers, cyclodextrins and cyclophanes: studies on the complexes, thermodynamic and kinetic parameters, effect of the structure of the guest and of the solvent: the hydrophobic effect.
Anion complexation by natural and synthetic receptors.
Self-assembly. Supramolecular catalysis.
Cavitands from cyclotriveratrylene, resorcarenes and calixarenes in molecular recognition. Calixarenes as molecular platform for the synthesis of receptors for cations, anions and neutral molecules.
Discussion on some application in the field of Supramolecular Science: Ion-selective Electrodes (ISE), ion-selective membranes, chromoionophores, piezoelectric and fluorescence sensors.
The following book represents a fair introduction to supramolecular chemistry.
Supramolecular Chemistry, P.D. Beer, P. A. Gale, D.K. Smith, Oxford University Primers, OUP, 1999.
For several topics should however be implemented with the following monographies:
Supramolecular Chemistry: Concepts and Perspectives. J.-M. Lehn, VCH Ed., Weinheim, 1985.
Comprehensive Supramolecular Chemistry. Executive editors Jerry L. Atwood...[et al.] ; chairman of the editorial board Jean Marie Lehn. - [Oxford] : Pergamon, 1996. - 11v.
Calixarenes Revisited. C.D. Gutsche, J.F. Stoddart Ed., Royal Society of Chemistry, Cambridge, 1998.
Container molecules and their guests. D.J. Cram and J.M. Cram. - London : Royal Society of Chemistry, 1994.
Crown ethers and cryptands. G.W. Gokel. - London : Royal Society of Chemistry, 1991.
Cyclophanes. F. Diederich. - London : Royal Society of Chemistry, 1991
The student will be evaluated (oral exam only) both on the monographic part and on the report on a literature article on a specific argument of supramolecular chemistry.