Synthesis of LnII‐in‐Cryptand Complexes by Chemical Reduction of LnIII‐in‐Cryptand Precursors: Isolation of a NdII‐in‐Cryptand Complex

Huh, Daniel N.; Ciccone, Sierra R.; Bekoe, Samuel; Roy, Saswata; Furche, Filipp; Evans, William J.

doi:10.1002/ange.202006393

Cited by 4 publications

(1 citation statement)

References 61 publications

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“…Soon after, Tm II in the crown ether complex [TmI 2 (18‐crown‐6)] ( 19 ) was found to display field induced slow relaxation of magnetization [35c] . Very recently the isolation of a Nd II in a cryptand complex was reported [Nd(OTf) 2 (crypt)] ( 20 ), isolated via the chemical reduction of the Nd II cryptand precursor [68b] …”

Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox‐active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox‐activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid‐based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox‐active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox‐activity in pre‐existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox‐activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.

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Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds

Ito

2022

Chemistry A European J

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The positive muon (μ+) can be regarded as a light isotope of proton and has been an important tool to study radical reactions of organic compounds. Recently, muons have been applied to produce short‐lived paramagnetic species from the heavier unsaturated organic molecules including the p‐block elements. This article overviews recent muon spin rotation/resonance (μSR) studies on the phosphorus analogs of alkenes, anthracenes, and cyclobutane‐1,3‐diyls together with the fundamentals of μSR. The acyclic phosphaalkene of P=C and phosphasilenes of P=Si can accept muonium (Mu=[μ+e−]) at the heavier double bonds, and the corresponding radicals have been characterized. The phosphorus atom in 9‐phosphaanthracene, whose P=C double bond is stabilized by the peri‐substituted CF3 groups, predominantly captures muonium to provide the corresponding paramagnetic fused heterocyclic system. The peri‐trifluoromethyl groups are functional to promote the unprecedented light isotope effect of muon providing the planar three‐cyclic molecular structure to consume the increased zero‐point energy. The formally open‐shell singlet 1,3‐diphosphacyclobutane‐2,4‐diyl unit can accept muonium at the (ylidic) phosphorus or the skeletal radicalic carbon, and the corresponding paramagnetic phosphorus heterocycles can be characterized by μSR. The findings on these muoniation processes to the unsaturated phosphorus‐containing compounds will contribute not only to development of novel paramagnetic functional species but also to progress on muon science.

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Solid-state and solution-phase characterization of Sm^II-aza[2.2.2]cryptate and its methylated analogue

et al. 2022

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Synthesis of Ln^II‐in‐Cryptand Complexes by Chemical Reduction of Ln^III‐in‐Cryptand Precursors: Isolation of a Nd^II‐in‐Cryptand Complex

Cited by 4 publications

References 61 publications

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds

Solid-state and solution-phase characterization of Sm^II-aza[2.2.2]cryptate and its methylated analogue

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Synthesis of LnII‐in‐Cryptand Complexes by Chemical Reduction of LnIII‐in‐Cryptand Precursors: Isolation of a NdII‐in‐Cryptand Complex

Cited by 4 publications

References 61 publications

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds

Solid-state and solution-phase characterization of SmII-aza[2.2.2]cryptate and its methylated analogue

Contact Info

Product

Resources

About

Synthesis of Ln^II‐in‐Cryptand Complexes by Chemical Reduction of Ln^III‐in‐Cryptand Precursors: Isolation of a Nd^II‐in‐Cryptand Complex

Solid-state and solution-phase characterization of Sm^II-aza[2.2.2]cryptate and its methylated analogue