Learning objectives
D1 - Knowledge and ability to understand
The student will be able to describe the main intermolecular interactions responsible for the structural organization in the crystals. She will understand and predict the relationships between structure and properties of crystalline materials. He will know the problems related to the prediction of crystalline structures, also in relation to intellectual property. She will know the model of supramolecular synthons, the classification and exemplification of structural motifs common in the solid state for organic / inorganic hybrid compounds. He will know the stereochemical requirements for the design of supramolecular coordination compounds in the form of polyhedral aggregates, monodimensional, two-dimensional, three-dimensional polymeric motifs. She will know the Cambridge Structural Database for the analysis of structural motifs in crystalline compounds and for data mining.
D2 - Ability to apply knowledge and understanding
The student will have the ability to analyze and interpret the three-dimensional structure of a crystal, in terms of geometry, symmetry and energy. She will have the ability to use crystallographic databases for data mining. He will have the ability to predict and design the most common three-dimensional assembly methods. She will be able to set up a crystallization process, planning the necessary parameters.He will know the use of single crystal X-ray diffraction.
D3 - Autonomy of judgment
The student will be able to independently evaluate the structure-property correlations using the most modern data mining and structural analysis techniques. He will know the fields and limits of use of diffraction techniques.
D4 - Communicative skills
The student will be able to find information and communicate on problems related to structural chemistry.
D5 - Learning skills
The student will be able to retrieve information through databases and the web, and will be able to continue to independently study the subject of structural chemistry.
Prerequisites
Basic knowledge of solid state chemistry.
Course unit content
Physical nature of the interactions between molecules: electrostatic, dispersive and repulsive contributions.
Origin of symmetry and periodicity in the structure of molecular crystals.
Main intermolecular interactions responsible for structural organization in molecular crystals.
Description of the role of interactions in the self-assembly of molecules through the model of supramolecular synthons.
Classification and exemplification of common structural motifs in the solid state for molecular and polymeric compounds, with particular attention to MOF and coordination polymers.
Crystallographic databases in crystal engineering
Tutorials: use of the Cambridge Structural Database for the analysis of structural motifs in crystalline compounds.
Crystallization: main descriptive models for nucleation and growth of molecular crystals.
Full programme
Nature of interactions between molecules. Principle of compact packaging in molecular crystals. Symmetry. Principle of Kitaigorodskii's Aufbau for the rationalization of structural reasons.
• Major intermolecular interactions responsible for structural organization in crystals: electrostatic interactions, conventional hydrogen bonding, weak hydrogen bonding, interactions between p-type systems, metal-to-metal interactions, interactions between halogens, interdigitation between aromatic rings.
• supramolecular synthons.
• Classification and exemplification of structural motifs common to the solid state for organic / inorganic hybrid compounds: networks of coordination compounds assembled by hydrogen bonding, diamondoid nets, infinite inorganic helixes, coordination polymers, porous solids. Interpenetration problem.
• Stereochemical requirements for the design of supramolecular coordination compounds in the form of polyhedral aggregates, monodimensional, two-dimensional, three-dimensional polymer motifs.
. Crystallographic databases in crystal engineering
• Tutorials: use of the Cambridge Structural Database for the analysis of structural motifs in crystalline compounds.
Porous materials: MOF, COF, porous non covalent networks.
Crystallization: Classical Nucleation Theory and Two Step Theory. The concept of solubility and supersaturatio. Nucleation, critical nuclei in the Classical Nucleation Theory. Nucleation in polymorphic systems. Crystal growth mechanisms. Mass transport and morphology. Characterization techniques.
Bibliography
Crystal Engineering: A Textbook
Gautam R. Desiraju, Jagadese J. Vittal, Arunachalam Ramanan, World Scientific Publishing Co Pte Ltd ( 2011)
Scientific literature ad hoc for specific subjects
Teaching methods
Lectures (52 h), comprising exercises on databases
Assessment methods and criteria
You can opt for an exam made by two partial tests, or for an oral exam.
Partial tests: 1. written discussion of a crystalline structure in geometric and energetic terms; 2. oral discussion of a question about crystallization processes. The final mark is the average of the two marks.
Oral exam for the assesment of knowledge and understanding, ability to apply knowledge, autonomy of judgment, and communication skills. The test is divided into three questions, one relating to intermolecular interactions, one relating to crystal engineering, one relating to crystallization. The evaluation scale is divided into: 18-23 = knowledge of the interactions and methods of assembly of crystalline materials; 24-27 = ability to discuss the possibilities of design and prediction of the structural assembly, also through computational and data mining methods; 28-30 = demonstration of critical autonomy in the understanding of the thermodynamic and kinetic factors responsible for obtaining a crystalline product. The trial lasts 30-40 minutes.
Other information
The slides of all lectures may be downoladed from the Elly portal.
Tutorials, examples, applications for molecular graphics software are also available.
2030 agenda goals for sustainable development
This teaching contributes to the realization of the UN objectives of the 2030 Agenda for Sustainable Development, SDG4 Quality Education.
