Decorated Tetrathiafulvalene‐Based Ligands: Powerful Chemical Tools for the Design of Single‐Molecule Magnets

• Published in: European journal of inorganic chemistry Vol. 2020; no. 2; pp. 148 - 164
• Main Authors: Cador, Olivier, Le Guennic, Boris, Ouahab, Lahcène, Pointillart, Fabrice
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 16.01.2020; Wiley-VCH Verlag
• Subjects: Chemical Sciences; Coordination chemistry; Coordination compounds; Dilution; Inorganic chemistry; Isotopic enrichment; Lanthanides; Ligand design; Ligands; Magnetic properties; Magnets; Optical properties; Organic chemistry; Oxidation; Photophysics; Quantum computing; Single‐molecule magnets; Tetrathiafulvalene; Ligand design; Single-molecule magnets; Tetrathiafulvalene; Photophysics; Lanthanides
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201900981

This Minireview covers the design and characterization of coordination lanthanide complexes involving TTF‐based ligands. The specific design of TTF‐based ligands allowed the isolation of complexes with magnetic properties such as Single‐Molecule Magnets (SMMs) behavior and the studies of magnetic modulations due to supramolecular interaction, molecular engineering, magnetic dilution as well as isotopic enrichment. A careful design leads to TTF‐based ligands displaying several coordination sites in order to rationally elaborate polynuclear systems with multi‐SMM behavior or to auto‐assembly SMMs. Their redox activity allowed the investigation of coordination lanthanide complexes in several oxidation states and their consequences on optical and magnetic properties. The complete experimental and theoretical studies of such systems contributed to the understanding of the magnetic properties of lanthanide ions for futures applications in high density storage and quantum computing. A library of TTF‐based ligands was elaborated from a common molecular skeleton through alkylation by chelating, paramagnetic, and chiral arms. With this library, lanthanide complexes were designed to understand the effects of supramolecular interaction, electronic distribution, and hyperfine coupling on SMM behavior. Multi‐SMM behavior as well as auto‐assembly of SMMs were rationally performed.