• D1-KNOWLEDGE AND UNDERSTANDING: the students will have to reach knowledge and understanding of the concepts, strategies, and analytical methods of Supramolecular Chemistry; the advantages/disadvantages and peculiarities of Supramolecular Chemistry compared to conventional covalent chemistry; the potential implementations of this interdisciplinary field towards the emergence of functional systems. • D2-APPLYING KNOWLEDGE AND UNDERSTANDING: the students will have to become familiar with the well-known classes of systems derived from the principles of supramolecular chemistry; understand the potential applications of these systems in various fields, like molecular recognition, confined reactivity, unidirectional motion. Clear view of the eligible techniques for analyzing and stimulating functional supramolecular systems. • D3-MAKING JUDGMENTS: the students will have to acquire the skills to read, comprehend, and discuss with critical attitude the scientific papers of the literature in the field of supramolecular chemistry. • D4-COMMUNICATION SKILLS: the students will have to acquire the skills to present and contextualize the content of a scientific paper from the literature in the field of supramolecular chemistry; and to acquire the capability to connect to adjacent contents and highlight possible perspectives. • D5-LEARNING SKILLS: at the end of the course the students will be able to autonomously tackle topics of Supramolecular Chemistry beyond the ones exposed during the course and will have the skills to handle the continuously growing state-of-the-art of this wide interdisciplinary subject.

• Basic and intermediate knowledge of coordination, organic and physical chemistry, including characterization analytical methods, typically acquired during the Bachelor Degree in Chemistry, and in parallel courses of the Master Degree in Chemistry. • Lectures with Power Point presentations (ppt). • Critical reading and discussion of scientific papers on most of the program section (also as self-test in preparation for the exam). • Highlights and references to supplemental materials. • Few hours (two up to four) by an external Italian or foreign professor on a specific topic within the field of Supramolecular Chemistry.

• Introduction and Bibliography; Concepts of complementarity, pre-organization, emerging properties and dynamic systems; Types of weak non-covalent interactions (e.g. dipole-charge, H-bonding, halogen bonding, hydrophobic effect) – the toolbox in supramolecular chemistry. • Host-guest interactions – Receptors for Cations (e.g. crown ethers, calixarenes); for Anions (e.g. polyazamacrocycles); and for Neutral Molecules (e.g. cavitands, cyclodextrines); 3D Covalent Capsules and their use as Receptor and for Stimulated Delivering. • Analytical Methods in Supramolecular Chemistry – a general overview, with more focus on NMR spectroscopy. • The principles of self-assembly; 3D cage structures from H-bonding, Directional Bonding, Sub-Component and Naked ions self-assembly; Applications of self-assembled 3D cages in stabilization of reactive species, delivery and confined reactions. • Self-assembly of intertwined and interlocked structures (e.g. helicates, catenanes, and molecular knots). • Concepts and examples of operating molecular machines. • Snap-shot section on one monographic chosen topic (e.g. Out-of-equilibrium systems, Dynamic Combinatorial Chemistry, Measure of association constants).

• J. W. Steed and J. L. Atwood “Supramolecular Chemistry”. L. F. Lindoy and I. M. Atkinson “Self-Assembly in Supramolecular Systems”. • J. W. Steed, D. R. Turner, K. J. Wallace Core Concepts in Chemistry and Nanochemistry, Wiley, Chichester, 2007. • V. Balzani, M. Venturi and A. Credi “Molecular Devices and Machines”. • Jonathan W. Steed (Editor-in-Chief), Philip A. Gale (Editor-in-Chief), Wiley “Supramolecular Chemistry: From Molecules to Nanomaterials, 8 Volume Set”. • ON MOODLE: -Lecture Notes on most of the subject covered during the course; -Slides of the lectures; -Scientific papers discussed, pdf excerpts of these; -Supplementary useful materials and references.

1. Introduction, origin and inspiration, bibliography, program schedule, course material and final exam. The tool-box of non-covalent interactions, description and energetics: electrostatic, -, Cation-, Anion- and CH-, H-Bonding, Halogen-Bonding, Metal-Ligand Coordination, Reversible Covalent Bonding, hydrophobic and macrocyclic effects. 2. Cation binding: Crown-ethers, Criptands, Spherands. Thermodynamic versus Kinetic Selectivity. Some preparation strategies. Calix[n]arenes: a successful class of fluxional receptors, discussion of one literature example. Anion binding: Polyazamacrocycles and the anion binding zone, receptor with mixed binding groups. Simultaneous Cation and Anion receptors: Cascade, Independent, Zwitter-ionic. Discussion of one literature paper. 3. Analytical and Characterization Methods: general summarized overview of the classical experimental and modelling techniques – IR, UV-vis absorption and emission and NMR spectroscopies; X-ray diffraction, Cyclic voltammetry and Mass Spectrometry analysis, Isothermal Calorimetry. Highlights on some specific aspects, queries and solutions. 4. Receptor for Neutral Substrates: Resorc[n]arenes, self-folded and functional Cavitands; In-and-Out exchange process. Discussion of one literature example. Cyclodextrines, Curcurbiturils, multiple H-bonding Receptors. 5. 3D molecular Capsules: Covalent - Carcerands and Hemicarcerads. Intrinsic and Constrictive Binding, Stabilization of confined reactive species, guest delivery or encapsulation by stimulated gating. Discussion of one literature example. Self-assembled by H-bonding – Tennis ball, Molecular Cylinder. In-and-Out exchange process. Social Isomerism. Reactivity in the confined space. Discussion of one literature paper. 6. Assembling by Coordination bonds – Directional Bonding Approach versus Metal-Mediation by Naked Cations. Examples of 2D metalla-macrocycles. Cages by Molecular Paneling; In-and-Out exchange process. Template effect, stabilization of reactive species, reactivity in the confined space: examples from the vast literature reported by the group of M. Fujita. Discussion of one literature paper. Cages by The Symmetry Interaction Approach, chirality and catalysis within the confined space: examples from the vast literature reported by the group of K. Raymond. Cages by The Sub-component self-assembly. Examples from the vast literature reported by the group of J. K. Nitschke. Discussion of one literature paper. 7. Intertwined systems: double, triple and cyclic Helicates. Chemical Topology and Interlocked structures: Catenanes, Rotaxanes and Knots by Metal-templation, H-bonding, Charge-transfer - interactions, sub-component self-assembly, Halogen bonding, Anion- interactions. Discussion of two literature papers. 8. Molecular Machines: concepts and definitions. Examples based on catenane or rotaxane structures and operating by chemical, electrochemical or photochemical stimuli. Discussion of one literature paper. Hints on unidirectional motion and systems put of equilibrium and dynamic combinatorial chemistry.

• Lectures with Power Point presentations (ppt). • Critical reading and discussion of scientific papers on most of the program section (also as self-test in preparation for the exam). • Highlights and references to supplemental materials. • Few hours (two up to four) by an external Italian or foreign professor on a specific topic within the field of Supramolecular Chemistry.

• Each year, if possible, an Italian or foreign Professor expert in the field will give a snapshot on a specific subject of Supramolecular Chemistry (two up to four hours), within those detailed in the full-program. Lectures material, and scientific paper discussed, will be available on MOODLE.

• Oral exam: critical presentation of a literature paper chosen from the pool of articles discussed along the course; expansion of the discussion to adjacent and more general concepts of the subject. The evaluation grid adopted is as follows: - Excellent (30 - 30 cum laude): excellent knowledge of the topics, excellent language property, excellent analytical ability, ability to brilliantly apply theoretical knowledge to concrete cases. Very good (27 - 29): good knowledge of topics, remarkable language property, good analytical ability, ability to correctly apply theoretical knowledge to concrete cases. Good (24-26): good knowledge of major topics, fair language property, adequate ability to apply theoretical knowledge to concrete cases. Satisfactory (21-23): possession of the fundamental knowledge of the teaching but incomplete mastery of some main topics, satisfactory ownership of language, and sufficient ability to apply theoretical knowledge to concrete cases. Sufficient (18-20): minimal knowledge of the main topics of the teaching and technical language, limited ability to adequately apply theoretical knowledge to concrete cases. Insufficient: lack of acceptable content knowledge of various program topics.

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