UE Coordination and supramolecular chemistry

Goal: These lectures will introduce you into the world of coodination chemistry both on a synthetic and a physico-chemical points of view. 

Content:

I. General concepts in coordination chemistry

• Metal ions and ligands
• Nomenclature of complexes
• Geometry of complexes with different coordinence
• Isomerism in coordination compounds

 II. Thermodynamic and kinetic approaches of complexes in solution

• Formation constants: definition and experimental determination
• Chelate effect, a central concept in coordination and supramolecular chemistry
• Applications to supramolecular recognition of cations
• Inertia and lability, essential kinetic notions for understanding complexes reactivity
• Synthesis of complex dedicated ligands: crown-ethers, Schiff bases, polypyridine, ...

III. Electronic structure of metal complexes

• Counting electrons in complexes: the Green's method
• 16/18 electrons rule
• Reactions implying metal complexes
• Application to homogeneous catalysis

• From crystal field to ligand field
• Construction of Molecular Orbitals diagrams of octahedral metal complexes
• Insight into spectroscopic series

IV. Optical properties of metal complexes

• Spectroscopic terms of metal complexes including lanthanide complexes
• Electronic spectroscopy of metal complexes
• Emission of light by metal complexes

V. Magnetic properties of monometallic complexes

• Origins of the magnetic properties of metal complexes
• Magnetic susceptibility
• From Van Vleck equation to Curie law
• Departures from Curie law
• Spin Cross-Over phenomenon: from definition to applications

Article Analysis

Every student will study and present an article dealing with an application strongly related to the contents of the lecture.

Practical teachings:

Four topics of the lectures will be illustrated during four hours experimental work sessions:

• Synthesis and study of the luminescent properties of lanthanide complexes

• Biomimetic model of molybdic oxo-tranferase enzyme

• Synthesis and properties of a iron(II) spin Cross-Over compound [1]

• Syntheis and study of a mixed-valence compound

To anticipate the Lab work, the practical work is written by each student in a dedicated Labwork notebook [2].

[1] A. Vallée et al., J. Chem. Educ. 2013, 90, doi: 10.1021/ed4000487

[2] A. Eisenberg J. Chem. Educ. 1982, 59, 1045.

Prerequisites: Basics knowledge of general chemistry (electronic structure of the elements, thermochemistry...), in group theory and in coordination chemistry (general definitions, crystal field theory)

• Inorganic Chemistry by J. E. Huheey
• Inorganic Chemistry by D. Shriver and P. Atkins
• Supramolecular Chemistry by J. M. Lehn
• Molecular Magnetism by O. Kahn
• Electrons in Molecules by J. P. Launay and M. Verdaguer