Ateneo - UPO

Physical principles of modern nuclear magnetic resonance. Heteronuclear and multidimensional spectra for the structural determination of organic and inorganic molecules. Applications of field cycling relaxometry for the study of paramagnetic metal ion complexes as structural and diagnostic probes. Coordination chemistry of f elements. Advanced notions of stereochemistry. Supramolecular chemistry, principles and definitions, preorganization and complementarity. Non-covalent interactions, van der Walls forces, dipole-dipole interactions, ion-dipole and ion-ion interactions, the cases of hydrogen bonding and halogen bonding. Templated synthesis of catenanes and rotaxanes. Principles of crystal engineering and main organic synthons. Molecular machines in living beings and synthetic molecular machines. Principles of organometallic chemistry and homogeneous catalysis.

Lecture notes provided by the teacher and available on DIR platform. Recommended reading:
On line course: http://www.cis.rit.edu/htbooks/nmr/inside.htm (J.P. Hornak);
H. Friebolin, "Basic One- and Two-Dimensional NMR Spectroscopy", VCH (available in the library)
- Huheey, Keiter, Keiter, Chimica Inorganica, Piccin
- J. W. Steed and J. L. Atwood, Supramolecular Chemistry, John Wiley & Sons, Chichester, 2rd edn, 2009.
- G. A. Jeffrey, An introduction to hydrogen bonding, Oxford university press, New York, 1997.
- G. R. Desiraju, J. J. Vittal, A. Ramanan, Crystal Engineering: A Textbook, World Scientific, Singapore 2011
Scientific papers will be given for further reading.

Solid basis of the advanced principles of pulse nuclear magnetic resonance spectroscopy. Knowledge of the main pulse sequences. Basic principles of the spectra in the solid state and of MRI. Using relaxometric techniques to study the properties of complexes of paramagnetic ions and their interaction with biomolecules. Ability of interpretation of mono- and bi-dimensional spectra of organic molecules and inorganic compounds based on the theoretical concepts.
Knowledge of the relevant chemical properties of the f elements in the context of modern applications. Become familiar with the basics of organometallic compounds and homogeneous catalysis. Fundamentals of supramolecular chemistry and concepts such as self-assembly, preorganization and complementarity. Advanced elements of stereochemistry. Familiarity with metal-templated syntheses and with the principles of molecular machines in the biological world and synthetic molecular machines. Acquire an overview of supramolecular chemistry in the solid state and its main applications.
Communication skills: the students will be able to use a suitable chemical vocabulary in relation to the topics described in the course and to write report on the result obtained from the application of these techniques. He will develop the ability in making judgements and autonomously deepen the arguments treated in the course.

Content of Inorganic, Organic, and Physical Chemistry courses. Basic knowledge of the main spectroscopic techniques.

Lectures integrated with some exercises in class and/or experiments on spectrometers and related discussion and data analysis. The optical and magnetic properties of the complexes of f elements and their use in biomedicine are the object of specific seminars and left to an independent learning process by students.

The main topics of the course will be discussed collectively in the classroom and applied directly during exercises in class (interpretation of NMR spectra) and on spectrometers.
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https://www.uniupo.it/en/services/servicesstudents-physical-or-learning-disabilities.
Students with disabilities, learning disabilities or special education
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concerning academic aspects.

Written exam consisting of: 6 open questions on the most relevant topics (18 points); assignment of 1H and 13C spectra of an molecule based on 1D and 2D experimental data (6 points). The results of the exam clarify the understanding of theoretical concepts, the ability to use them to solve problems of medium difficulty, the skill of making judgements and the knowledge of an appropriate technical-scientific language. The student will pass the exam with the knowledge of the basic concepts (13/24) and will get the highest grade demonstrating all the listed abilities/capacities. Additional points relative to the laboratory report will be added to the score achieved with the written exam (up to max. 6; see Syllabus of the joined course).

Spectroscopic methods based on magnetic resonance for the study of molecular structure and dynamic processes. First- and second-order NMR spectra. Relaxation times: definition, measures and mechanisms. Modern techniques: 1) double resonance: broadband decoupling (gated and off-resonance); 2) NOE: principles and applications; 3) INEPT and DEPT sequences. 2D NMR: general and homo- and heteronuclear experiments (COSY, EXSY, NOESY, HMQC, HMBC). Dynamic NMR: general information, line-shape analysis, kinetic parameters, applications. NMR and the Periodic Table: applications in inorganic chemistry. Solid state NMR: general principles and applications. NMR of paramagnetic systems: metal ions, complexes and conjugates to macromolecules. Relaxometric techniques and fast- field cycling relaxometry. Principles of MRI and use of metal systems as contrast agents. Principles of stereochemistry, chirality, symmetry elements, axis and plane chirality, enantiomers, diastereomers, resolution of enantiomers by fractional crystallization with chiral agents. Supramolecular chemistry: key concepts and definitions, preorganization and complementarity, self-assembly and key-lock concept. Non-covalent interactions, principles and properties: van der Walls interactions, Lennard-Jones potential, ion-dipole and ion-ion interactions. Dipole-dipole interactions: the cases of hydrogen bonding and halogen bonding. Recall of acidity and basicity, Brønsted and Lewis superacids. Templated synthesis: macrocycles, catenanes and rotaxanes. Molecular machines in the biological world: Actin, Kinesin, Dynein and ATP Synthase. Synthetic molecular machines based on catenanes and rotaxanes: molecular shuttles and elevators. Crystal engineering: purposes, definitions and presentation of the main organic synthons. Metal-organic porous solids: coordination polymers and MOFs, applications in the field of storage, separation and molecular recognition. Organometallic chemistry: carbonyls, metallocenes, metal clusters; characteristic reactions. Catalysis: metathesis and hydrogenation of alkenes, hydroformylation, oxidation, formation of C-C bonds, oligomerizations and polymerizations. The coordination chemistry of the f elements: oxidation states, occurrence and recovery; optical and magnetic properties; coordination compounds.

Knowledge and understanding: knowledge of the most common NMR techniques and their applications; knowledge of the principles useful to assign and/or predict 1H and 13C NMR spectra of organic molecules and simple inorganic molecules. Knowledge of the basic principles of supramolecular chemistry, preorganization, complementarity and self-assembly. Knowledge of the fundamentals of the design of organic and organometallic solids. Familiarity with the main chemical characteristics of organometallic compounds of d and f blocks and their applications in organic synthesis and industrial catalysis.
Applying knowledge and understanding: ability to apply the theory to the interpretation of NMR spectra (ability to assign and/or predict 1H and 13C NMR spectra of organic molecules and simple inorganic molecules), to the analysis of the 1H and 13C relaxation times and to explanation of temperature-dependent phenomena. Ability to predict the self-assembly of organic molecules in the solid state starting from the structure of the simple synthons involved. Ability to use knowledge of structure and bonding in organometallic compounds to interpret their role in catalysis.
Making judgements: skill to critically evaluate the concepts learnt.
Communication skills: ability to use appropriate scientific language in answering questions and analyzing spectral data; achievement of a suitable scientific language to communicate in a correct, concise and clear manner.
Learning skills: ability to use the teaching material for a critical study that allows the possibility of an autonomous acquisition of further knowledge in the field of NMR spectroscopy and the most advanced applications of inorganic and supramolecular chemistry.