CHM682A

Modern Chemistry and Applications of Lanthanides

CHM682A

3-0-0-9

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Prerequisites: None

Course Contents

Topics

Introduction to Lanthanide chemistry: Discovery, extraction and separations, position in periodic table, Highlights of f-block elements, Differences from d-block/main group elements, why RE’s are critical elements? Rare earths in modern technologies, Technical sustainable recycling of Lanthanides (No. of Lecture 3)

Principles, energetics and Periodic properties f-block elements: principles, energetics, periodic properties and trends, f-orbitals, lanthanide contraction, ionic radii, oxidation states, stability (No. of Lecture 4)

Coordination Chemistry of Lanthanides: Binary compounds, Cerium oxide and uses, Complexes, nature of bonding, hydration & hydrolysis, stability of complexes, ligand types and their design, geometry and structures of Ln-complexes, Structure-property relationships, Heterometallic lanthanide systems, f-f, f-f’, d-f, s-f hybrid multimetallic systems (No. of Lecture 6)

Organometallic Chemistry of Lanthanides: bonding, alkyls, aryls, arenes, synthesis, structure and reactivity, application of organo-lanthanide compounds in organic transformation, divalent rare earth chemistry, catalytic applications: sigma bond metathesis, olefin hydrogenation/Ziegler-Natta catalysis, Hydroamination reactions (No. of Lecture 5)

Spectroscopic properties of Lanthanides: Basic f-element electronic structures, Excited state electronic properties, luminescence properties, nature of f-f transitions, sensitization mechanism: antenna effect, energy-transfer, time-resolved luminescence spectroscopy, Upconversion of Ln-luminescence, Ln-probes for bioresponsive imaging and design principles, luminescence-based applications (No. of Lecture 6)

Luminescence-based Chemosensors and Bio-imaging with Lanthanide Complexes: Modulation of lanthanide luminescence and quenching, Chemosensor design principle, Time-resolved luminescence, Ln-based bioimaging, cellular imaging probes, Emissive lanthanide probes studying protein interactions (No. of Lecture 6)

Magnetic properties of Lanthanides: Electronic structures, term symbols, spin-orbit coupling, magnetic moments, permanent magnets, NMR-shift reagents, Lanthanide Single-molecule-magnet (SMM), Superconductive materials (No. of Lecture 4)

Lanthanide-base MRI Contrast Agents: Principles of MRI, Contrast agents, Gadolinium-chelates as MRI contrast agents, water-exchange kinetics, Relaxivity, relaxation time, molecular parameters for relaxivity in MRI probes, Sensitivity and Selectivity of MRI probes, New generation MRI contrast agents (No. of Lecture 3)

Lanthanides in Biology: Bioinorganic chemistry of Ln, Emergence of lanthanide in metallobiochemistry and microbiology, Ln-dependent proteins: methanol dehydrogenase (MDH), lanmodulin as selective Ln-binding protein, mechanism of uptake by bacteria (No. of Lecture 3)

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Recommended books:

Lanthanide and Actinide Chemistry, Simon Cotton, John Wiley & Sons, Ltd. 2006.
Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials, Ed. Ana de Bettencourt–Dias , John Wiley and Sons, Ltd, 2014
Lanthanide-Based Multifunctional Materials, Ed. P. Martin-Ramos, M. Ramos-Silva, Elsevier 2018
Lanthanide Luminescence: Photophysical, Analytical and Biological Aspects, Ed. P. Hänninen, H. Härmä, Springer, 2011
Lanthanides and Actinides in Molecular Magnetism, Ed. R. A. Layfield, M. Murugesu, Wiley-VCH, 2015

Reference Materials:

J.-C. G. Bünzli, Lanthanide Luminescence for Biomedical Analyses and Imaging, Chem. Rev. 2010, 110, 2729-2755.
D. Parker, R. S. Dickins, H. Puschmann, C. Crossland, J. A. K. Howard, Being Excited by Lanthanide Coordination Complexes: Aqua Species, Chirality, Excited-State Chemistry, and Exchange Dynamics, Chem. Rev. 2002, 102, 1977-2010.
D. Parker and J. A. G. Williams, Getting excited about lanthanide complexation chemistry, J. Chem. Soc., Dalton Trans. 1996, 3613-3628.
M. C. Hefferen, L. M. Matosziuk, T. J. Meade, Lanthanide Probes for Bioresponsive Imaging, Chem. Rev. 2014, 114, 4496-4539.
L. J. Daumann, Essential and Ubiquitous: The Emergence of Lanthanide Metallobiochemistry, Angew. Chem. Int. Ed. 2019, 58, 12795-12802.

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