Genuine Redox Isomerism in a Rare‐Earth‐Metal Complex

Fedushkin, Igor L.; Maslova, Olga; Morozov, A. G.; Dechert, Sebastian; Demeshko, Serhiy; Meyer, Franc

doi:10.1002/anie.201204452

Cited by 125 publications

(65 citation statements)

References 14 publications

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“…2b) 64 . Because of the metal-to-ligand charge transfer, the redox state of the metal centres in the dinuclear Yb 2 complex changes from Yb III Yb III at LT to Yb III Yb II at HT.…”

Section: Charge Transfermentioning

confidence: 98%

Dynamic molecular crystals with switchable physical properties

2016

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The development of molecular materials whose physical properties can be controlled by external stimuli - such as light, electric field, temperature, and pressure - has recently attracted much attention owing to their potential applications in molecular devices. There are a number of ways to alter the physical properties of crystalline materials. These include the modulation of the spin and redox states of the crystal's components, or the incorporation within the crystalline lattice of tunable molecules that exhibit stimuli-induced changes in their molecular structure. A switching behaviour can also be induced by changing the molecular orientation of the crystal's components, even in cases where the overall molecular structure is not affected. Controlling intermolecular interactions within a molecular material is also an effective tool to modulate its physical properties. This Review discusses recent advances in the development of such stimuli-responsive, switchable crystalline compounds - referred to here as dynamic molecular crystals - and suggests how different approaches can serve to prepare functional materials.

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“…2b) 64 . Because of the metal-to-ligand charge transfer, the redox state of the metal centres in the dinuclear Yb 2 complex changes from Yb III Yb III at LT to Yb III Yb II at HT.…”

Section: Charge Transfermentioning

confidence: 98%

Dynamic molecular crystals with switchable physical properties

2016

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“…While redox-active ligands have been proven to impart interesting magnetic [8,9] or electrochemical [10][11][12] properties to the rare earth elements due to their ability to stabilize ligand radicals, [13,14] fewer examples exist that demonstrate productive electron movement for new bond formation. Mazzanti et al reported tetradentate Schiff base complexes of Nd, Eu, Tb,Ybthat, upon reduction, store two electrons in anew CÀC s bond.…”

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confidence: 99%

Neodymium(III) Complexes Capable of Multi‐Electron Redox Chemistry

2017

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A family of neodymium complexes featuring a redox-active ligand in three different oxidation states has been synthesized, including the iminoquinone (L ) derivative, ( iq) NdI (1-iq), the iminosemiquinone (L ) compound, ( isq) NdI(THF) (1-isq), and the amidophenolate (L ) [K(THF) ][( ap) Nd(THF) ] (1-ap) and [K(18-crown-6)][( ap) Nd(THF) ] (1-ap crown) species. Full spectroscopic and structural characterization of each derivative established the +3 neodymium oxidation state with redox chemistry occurring at the ligand rather than the neodymium center. Oxidation with elemental chalcogens showed the reversible nature of the ligand-mediated reduction process, forming the iminosemiquinone metallocycles, [K(18-crown-6)][( isq) Nd(S )] (2-isq crown) and [K(18-crown-6)(THF)][( isq) Nd(Se )] (3-isq crown), which are characterized to contain a 6-membered twist-boat ring.

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“…To the besto fo ur knowledge, the reactiono ft his ligand with lanthanide halogenides has so far not been reported in a3:1 stoichiometry. [13] Notably,s imilar vanadium complexes with ar elated ligand have been described previously. [14] As summarized in Scheme 1, the Ln(Ph-BIAN) 3 compounds were obtained in high yields.…”

Section: Resultsmentioning

confidence: 99%

A New Class of Lanthanide Complexes with Three Ligand Centered Radicals: NMR Evaluation of Ligand Field Energy Splitting and Magnetic Coupling

Hiller

Sittel

Wadepohl

et al. 2019

Chemistry A European J

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Combination of three radical anionic Ph‐BIAN ligands (Ph‐BIAN=bis‐(phenylimino)‐acenaphthenequinone) with lanthanoid ions leads to a series of homoleptic, six‐coordinate complexes of the type Ln(Ph‐BIAN)3. Magnetic coupling data were measured by paramagnetic solution NMR spectroscopy. Combining 1H NMR with 2H NMR of partially deuterated compounds allowed a detailed study of the magnetic susceptibility anisotropies over a large temperature range. The observed chemical shifts were separated into ligand‐ and metal‐centered contributions by comparison with the Y analogue (diamagnetic at the metal). The metal‐centered contributions of the complexes with the paramagnetic ions could then be separated into pseudocontact and Fermi contact shifts. The latter is large within the Ph‐BIAN scaffold, which shows that magnetic coupling is significant between the lanthanide ion and the radical ligand. Pseudocontact shifts were further correlated to structural data obtained from X‐ray diffraction experiments. Ligand‐field parameters were determined by fitting the temperature dependence of the observed magnetic susceptibility anisotropies. The electronic structure determined by this approach shows, that the Er and Tm analogues are candidates for single molecule magnets (SMM). These results demonstrate the possibilities for the application of NMR spectroscopy in investigations of paramagnetic systems in general and single molecule magnets in particular.

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Genuine Redox Isomerism in a Rare‐Earth‐Metal Complex

Cited by 125 publications

References 14 publications

Dynamic molecular crystals with switchable physical properties

Dynamic molecular crystals with switchable physical properties

Neodymium(III) Complexes Capable of Multi‐Electron Redox Chemistry

A New Class of Lanthanide Complexes with Three Ligand Centered Radicals: NMR Evaluation of Ligand Field Energy Splitting and Magnetic Coupling

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