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Open AccessReview

Smart Ligands for Efficient 3d-, 4d- and 5d-Metal Single-Molecule Magnets and Single-Ion Magnets

1
Department of Chemistry, University of Patras, 265 04 Patras, Greece
2
Institute of Chemical Engineering Sciences, Foundation for Research and Technology-Hellas (FORTH/ICE-HT), Platani, P.O.Box 1414, 265 04 Patras, Greece
*
Authors to whom correspondence should be addressed.
This work is devoted to Research Director Vassilis Psycharis on the occasion of his 60th birthday. Dr. Psycharis is an excellent structural scientist, a fantastic collaborator and a precious friend.
Received: 16 April 2020 / Revised: 20 May 2020 / Accepted: 21 May 2020 / Published: 29 May 2020
There has been a renaissance in the interdisciplinary field of Molecular Magnetism since ~2000, due to the discovery of the impressive properties and potential applications of d- and f-metal Single-Molecule Magnets (SMMs) and Single-Ion Magnets (SIMs) or Monometallic Single-Molecule Magnets. One of the consequences of this discovery has been an explosive growth in synthetic molecular inorganic and organometallic chemistry. In SMM and SIM chemistry, inorganic and organic ligands play a decisive role, sometimes equally important to that of the magnetic metal ion(s). In SMM chemistry, bridging ligands that propagate strong ferromagnetic exchange interactions between the metal ions resulting in large spin ground states, well isolated from excited states, are preferable; however, antiferromagnetic coupling can also lead to SMM behavior. In SIM chemistry, ligands that create a strong axial crystal field are highly desirable for metal ions with oblate electron density, e.g., TbIII and DyIII, whereas equatorial crystal fields lead to SMM behavior in complexes based on metal ions with prolate electron density, e.g., ErIII. In this review, we have attempted to highlight the use of few, efficient ligands in the chemistry of transition-metal SMMs and SIMs, through selected examples. The content of the review is purely chemical and it is assumed that the reader has a good knowledge of synthetic, structural and physical inorganic chemistry, as well as of the properties of SIMs and SMMs and the techniques of their study. The ligands that will be discussed are the azide ion, the cyanido group, the tris(trimethylsilyl)methanide, the cyclopentanienido group, soft (based on the Hard-Soft Acid-Base model) ligands, metallacrowns combined with click chemistry, deprotonated aliphatic diols, and the family of 2-pyridyl ketoximes, including some of its elaborate derivatives. The rationale behind the selection of the ligands will be emphasized. View Full-Text
Keywords: ligands; molecular magnetism; single-ion magnets (SIMs) or monometallic single-molecule magnets; single-molecule magnets (SMMs); synthetic strategies; 3d-, 4d- and 5d-metal complexes as SIMs and SMMs ligands; molecular magnetism; single-ion magnets (SIMs) or monometallic single-molecule magnets; single-molecule magnets (SMMs); synthetic strategies; 3d-, 4d- and 5d-metal complexes as SIMs and SMMs
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MDPI and ACS Style

Perlepe, P.S.; Maniaki, D.; Pilichos, E.; Katsoulakou, E.; Perlepes, S.P. Smart Ligands for Efficient 3d-, 4d- and 5d-Metal Single-Molecule Magnets and Single-Ion Magnets. Inorganics 2020, 8, 39. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8060039

AMA Style

Perlepe PS, Maniaki D, Pilichos E, Katsoulakou E, Perlepes SP. Smart Ligands for Efficient 3d-, 4d- and 5d-Metal Single-Molecule Magnets and Single-Ion Magnets. Inorganics. 2020; 8(6):39. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8060039

Chicago/Turabian Style

Perlepe, Panagiota S.; Maniaki, Diamantoula; Pilichos, Evangelos; Katsoulakou, Eugenia; Perlepes, Spyros P. 2020. "Smart Ligands for Efficient 3d-, 4d- and 5d-Metal Single-Molecule Magnets and Single-Ion Magnets" Inorganics 8, no. 6: 39. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8060039

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