Integrated Course in Molecular Design and Supramolecular Inorganic Chemistry

Module CHIMICA INORGANICA SUPRAMOLECOLARE

The course introduces the fundamentals of Supramolecular Chemistry, with particular focus on inorganic aspects, through the study of non-covalent interactions, self-assembly processes, and the role of metal ions in the formation of functional structures. Examples from biological and natural systems will be discussed to illustrate how supramolecular principles govern the construction of complex architectures. The course also presents the strategies of supramolecular design and how to translate theoretical principles into the synthesis of species with targeted chemical-physical properties.

In accordance with the Dublin Descriptors, the course contributes to the development of:

• Knowledge and understanding: Students will acquire knowledge of the fundamental principles of supramolecular chemistry, with particular emphasis on inorganic aspects. Self-assembly mechanisms, non-covalent interactions, the role of metal ions, and the thermodynamic and kinetic principles governing the formation of complex systems will be explored, highlighting the relationship between structure and function.
• Applied knowledge and understanding: Students will be able to apply the acquired principles to the design of supramolecular systems and to the evaluation of cases drawn from the scientific literature, linking theory and practice, interpreting experimental data, and using scientific terminology correctly.
• Judgement skills: Students will develop the ability to critically analyze results and models reported in the literature, assessing the coherence of supramolecular design strategies with the intended functional objectives. This skill is fostered through the preparation of individual presentations and in-class discussions.
• Communication skills: Students will be able to clearly and rigorously present concepts in inorganic supramolecular chemistry, using appropriate scientific communication tools, such as presentations, diagrams, and charts.
• Learning skills: The course promotes autonomous learning through the analysis of scientific articles and collective discussion of content. The ability to acquire, process, and apply knowledge will be assessed during the oral examination.

Information for Students with Disabilities and/or Specific Learning Disorders 

To ensure equal opportunities and in compliance with current legislation, interested students may request a personal meeting in order to arrange any compensatory and/or exemption measures, based on the learning objectives and their specific needs.

The teaching methods adopted in the Supramolecular Inorganic Chemistry module include lectures, interactive and/or cooperative learning activities, for a total of 21 hours, complemented by discussions and the analysis of case studies drawn from the scientific literature.

Practical exercises, individual research activities, and group work are also included, with the aim of promoting the critical application of acquired knowledge and the development of independent judgment and design skills.

The preparation of the individual presentation required for the final examination also provides an opportunity for independent study and for applying the knowledge and skills developed throughout the course.

1. Introduction to Supramolecular Chemistry

• Positive and negative cooperativity in supramolecular systems.
• Factors determining complex stability and selectivity.
• Hofmeister (lyotropic) series.

2. Cation Recognition

• Principles for the design of cation receptors.
• Relationship between cation size, cavity geometry, and the nature of donor atoms.
• HSAB theory applied to ion recognition.
• Natural and biomimetic cation receptors.
• Crown ethers, cryptands, spherands, calixarenes, and other macrocyclic receptors.
• Schiff-base macrocycles and template synthesis.
• Recognition of alkali metals, alkaline-earth metals, transition metals, and soft metal ions.
• Siderophores and natural systems for iron recognition and transport.
• Porphyrins and porphyrinoids.

3. Anion Recognition

• Anion properties relevant to supramolecular recognition.
• Differences between cation and anion recognition.
• Design strategies for anion receptors.
• Hydrogen bonding, electrostatic interactions, and other directional interactions.
• Effects of geometry, basicity, charge density, solvation, and counterions.
• Acyclic and macrocyclic receptors.
• Metal complexes as anion receptors.
• Lanthanide complexes for the recognition and sensing of anionic species.
• Recognition of phosphate, pyrophosphate, and other biologically relevant anions.

4. Simultaneous Recognition of Cations and Anions

• Heteroditopic receptors.
• Ion-pair recognition.
• Cascade complexes.
• Zwitterion recognition.
• Cooperativity and allostery in simultaneous recognition.
• Importance of distance and geometry between binding sites.
• Examples involving amino acids, phosphates, and ion pairs.

5. Metal-Directed Supramolecular Self-Assembly

• Principles of self-assembly: reversibility, thermodynamic control, and the role of building blocks.
• Self-assembly driven by non-covalent interactions.
• 0D, 1D, 2D, and 3D systems.
• Template effect and metal-directed self-assembly.
• Relationship between metal coordination geometry and supramolecular architecture.
• Metallocycles, metallocages, and polyhedral structures.
• Edge-directed and face-directed self-assembly.
• Coordination polymers and Metal–Organic Frameworks (MOFs).
• Comparison between metallocycles, metallocages, and MOFs.

6. Applications of Supramolecular Inorganic Chemistry

• Optical, fluorescent, and electrochemical ion sensors.
• Indicator displacement assays.
• Ion transport across membranes.
• Extraction, separation, and recovery of ionic species.
• Supramolecular catalysis and biomimetic enzyme models.
• Biomedical applications of supramolecular receptors.
• Imaging and sensing of biologically relevant species.
• Drug delivery and applications of metallocages and MOFs.

The course MOLECULAR DESIGN AND INORGANIC SUPRAMOLECULAR CHEMISTRY is divided into two distinct teaching modules, each with its own final exam. Passing both exams is required to earn the credits associated with the course. The final grade for the course is determined as the arithmetic average of the grades obtained in the two modules, expressed on a 30-point scale.

The exam for the Inorganic Supramolecular Chemistry module is divided into two parts, both contributing to the final grade:

1. Individual presentation with project (50% of the grade): the student prepares an oral presentation on a topic agreed with the instructor, including an original project of a supramolecular system. The assessment takes into account the ability to apply theoretical knowledge, critically analyze the literature, design solutions consistent with functional objectives, and communicate clearly and rigorously.
2. Theoretical discussion (50% of the grade): oral questions based on the course program, aimed at assessing the understanding of fundamental concepts, non-covalent interactions, self-assembly, and the role of metal ions in supramolecular systems.

Final grade for the Inorganic Supramolecular Chemistry module
The grade, expressed on a 30-point scale, reflects the overall evaluation of both parts, considering theoretical knowledge, applied skills, autonomy of judgment, clarity of presentation, and project-related competencies.

Concepts of complementarity and preorganization; Chelate effect; Macrocyclic and cryptate effects; Cooperativity; Techniques for the study of supramolecular systems; Hofmeister series; Receptors for cation binding; Receptors for anion binding; Explain the concept of self-assembly in Supramolecular Chemistry and describe how non-covalent interactions drive the formation of ordered structures; Provide an example of a natural or inorganic system in which self-assembly plays a fundamental role.