Ateneo - UPO

In the Advanced Inorganic Chemistry Module, the following subjects will be developed: 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.
The Advanced Inorganic Chemistry Laboratory aims at providing students with a better understanding of the coordination compounds, , also integrating the knowledge acquired during Advanced Inorganic Chemistry. In particular, the study of electron paramagnetic resonance spectroscopy (EPR) and its applications will be developed.

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.
- J. A. Weil, J. R. Bolton, Electron Paramagnetic Resonance: Elementary Theory and Practical Applications, Ed. John Wiley & Sons, 1994.
- M. Brustolon, E. Giamello, Electron Paramagnetic Resonance - A Practitioner’s Toolkit, Ed. John Wiley & Sons, Inc., Hoboken, New Jersey, 2009.

The Advanced Inorganic Chemistry Module aims to provide: 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.
The Advanced Inorganic Chemistry Laboratory aims to critically discuss some subjects of interest in the field of Inorganic Chemistry, with the application of consolidated methodologies and some advanced investigation techniques. The student will learn the theoretical bases of electron paramagnetic resonance (EPR), acquiring the ability to apply them to the coordination compounds, and theoretical bases on the use of metal complexes. The student will also acquire practical concepts on the methods employed in the laboratory about preparation, purification and characterization of the coordination compounds using advanced laboratory practice and instrumentation. The student will be able to apply the learnt methods and carry on the experiments autonomously; he will be able to collect, understand and critically discuss the data obtained from the characterization of the complexes explaining them based on the acquired knowledge.
The whole course wants to develop the ability in making judgements, drawing conclusions and autonomously deepening a subject related to those of the course.
Finally, the student will develop its communication skills using a suitable chemical vocabulary in relation to the topics of the course and he will write and then discuss a report on the result obtained from the application of these techniques.

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

Advanced Inorganic Chemistry Module: 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.
Advanced Inorganic Chemistry Laboratory: Introductory lectures (theoretical and practical concepts) and practical experiences in laboratory to apply the theoretical concepts of the course. The student will have to fill in a laboratory notebook and will work in group both during the laboratory experiences and when writing a report about them. Moreover, autonomously he will have to study in-depth a subject (related to the program) among those suggested by the teacher that will give him suitable scientific articles to be read.

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.
The ongoing learning during the Advanced Inorganic Chemistry Laboratory will be checked with the discussion of the experimental results at the end of the laboratory experiments.
- Students with physical disabilities, Learning Disabilities or Special Education Needs can request specific services and tools via the "Staff Sviluppo e Coordinamento Carriere e Servizi alle Studentesse e agli Studenti", consulting the University webpage: https://www.uniupo.it/en/services/servicesstudents-physical-or-learning-disabilities.

- Students with disabilities, learning disabilities or special education needs, once they have contacted the University Staff, can refer to the tutor in charge of the course to define the examination modalities, concerning academic aspects.

Written exam consisting of: 6 open questions on the most relevant topics (18 points); assignment of 1H and 13C spectra of a 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. Th 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.
The presence in the laboratory is compulsory and the student must fill in a laboratory notebook to develop the ability to correctly describe a carried-out experiment and collect data.
At the end of the laboratory the student will produce a written report on the experiences carried out, containing a critical analysis of the results obtained in the experiments to develop its skill to draw conclusions from the carried-out experiments and its communication skills. The report will also include a personal in-depth study about the topics of the laboratory part of the course. The submission of the report will be precondition for access to the written exam of the course and the report itself will be evaluated by the examination board, together with the exam, up to a maximum of 6 points.
Such a procedure of evaluation will allow to evaluate the acquired theoretical knowledge, the ability to apply them to real situations, the skill to collect and critically analyze the obtained results, the communication skills in the description of the carried-out work, the learning skills. The student with all the listed abilities/capacities (see expected learning outcomes) will be given the highest grade.

In the Advanced Inorganic Chemistry Module the spectroscopic methods based on magnetic resonance for the study of molecular structure and dynamic processes will be studied. 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.
The Advanced Inorganic Chemistry Laboratory aims at providing students with the basic knowledge of the electron paramagnetic resonance spectroscopy (EPR). The course consists of an introduction to this technique (theory and instrumentation) and its applications to metal complexes.
The laboratory experiments will follow this first part. In particular: synthesis and EPR characterization of a vanadium complex; the therapeutic application of nitric oxide; extraction determination of the catalytic properties of the metalloenzyme catalase; synthesis and oxygen absorption by a cobalt complex
These experiments could be replaced by others depending on the number of students or if the improvement of the course is necessary.

Knowledge and understanding: knowledge of the most used NMR techniques and their applications; knowledge of the principles for assigning 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 organic and organometallic solid design. Familiarity with the main chemical characteristics of organometallic compounds of the d and f blocks and their applications in industrial synthesis and catalysis. Knowledge of the basics of EPR spectroscopy, practical notions on the preparation, purification and characterization of coordination compounds using advanced methods and instrumentation.
Ability to apply knowledge and understanding: ability to apply theoretical knowledge to the interpretation of NMR spectra (ability to assign and/or predict NMR spectra of organic molecules and simple inorganic molecules), to the analysis of relaxation time values and to the 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.
Ability to collect data correctly and keep a laboratory notebook; ability to apply theoretical knowledge to the execution and understanding of laboratory experiments and the interpretation of the results obtained.
Making judgement: Ability to critically analyze the notions learned and evaluate the results obtained in practical experiences, identifying possible errors and proposing solutions
Communication skills: ability to use appropriate scientific language in answering questions, analyzing spectral data and reporting on the work carried out; acquisition of appropriate scientific language to communicate precisely, concisely and clearly.
Learning ability: ability to use the teaching material for a critical and reasoned study that allows the subsequent autonomous acquisition of further knowledge in the field of NMR spectroscopy and the most advanced applications of inorganic and supramolecular chemistry. Ability to independently delve into a topic related to those of the course and to analyze data, interpreting them in the light of the knowledge acquired.