Circularly polarized luminescence of lanthanide-based single-molecule-magnets – SMMCPL

The SMMCPL project aims at investigating both experimentally and theoretically the synergy between Single-Molecule Magnet (SMM) behaviour and Circularly Polarized Luminescence (CPL) in chiral lanthanide-based mononuclear complexes. Indeed, the magnetic-dipole f-f transitions responsible for the enhanced CPL response on f-block elements are anticipated to interact at low temperature with the internal magnetic field of a SMM. In order to examine the interplay between these two phenomena, i.e. SMM, a ground-state property, and CPL, an excited-state property, a multi- and interdisciplinary approach will be used. Enantiomerically pure Ln(III) complexes will be synthesized, either by introducing a chirality element in a ligand coordinated to an emissive Ln(III) ion or by generating chirality via the arrangement of the ligands around the luminescent centre. Then the luminescence and chiroptical properties (especially electronic circular dichroism (ECD) and CPL) will be studied in the UV-Vis and NIR regions depending on the lanthanide used. Concomitantly, the magnetic properties of the complexes, potentially SMM, will be investigated. The interplay between the magnetic properties and CPL activity will be studied by selecting appropriate lanthanide ion, and by performing CPL measurements at low temperature, i.e. at temperatures at which magnetic hysteresis loops are observed in SMM and finally by thoroughly analyzing the results using Quantum Chemistry (QC) approaches. The project will necessitate both the development of a local set-up for CPL measurements and of QC methodologies for the fine calculation of CPL data. The SMMCPL project will involve a unique combination of approaches (4 partners) in synthesis, coordination chemistry, magnetism, spectroscopy and theoretical chemistry, as well as in physics.