Electro‐Conductive Single‐Molecule Magnet Composed of a Dysprosium(III)‐Phthalocyaninato Double‐Decker Complex with Magnetoresistance

Sato, Takaaki; Breedlove, Brian K.; Yamashita, Masahiro; Katoh, Keiichi

doi:10.1002/ange.202102666

“…The conductive nature is due to partial hole doping of the Pc ligand, and the resulting small negative magnetoresistance is likely due to the negligible 4f−π interactions. 36 The high coordination numbers possible with lanthanoid ions cause SMM properties and large negative charges of their metal complexes. Therefore, more organic conductors (donors) are necessary to neutralize the negatively charged SMMs, and the resulting intermolecular interactions between conductors or components become enhanced.…”

Section: ■ Introductionmentioning

confidence: 99%

4f−π Molecular Hybrid Exhibiting Rich Conductive Phases and Slow Relaxation of Magnetization

Shen

¹

,

Cosquer

²

,

Zhang

³

et al. 2021

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Cooperation between single-molecule magnets and electrical conductivity holds promise for preparing high-density magnetic devices; however, there are only a few reports so far. Here we report a 4f−π-based molecular hybrid, k-(ET)5Dy(NCS)7(KCl)0.5 (1) (ET = bis(ethylenedithio)tetrathiafulvalene, NCS = thiocyanate), which undergoes slow relaxation of the magnetization and electrical conductivity. Unlike common ET-based conductive salts, K+ ions were intercalated into ET layers and coordinated with ET radicals. We found that the ET charges were sensitive to temperature, resulting in rich conductive phases at 75–300 K. In particular, the upturn in conductivity with a clear hysteresis loop was explained by the formation of partially oxidized states with charges close to 0.5+, which accounts for a metallic state. From the results of electronic structure calculations, the hole concentration increased to 125 K, which is consistent with a partially oxidized state upon cooling. The weak antiferromagnetic interactions accompanied by a dual magnetic relaxation process below 4 K are closely associated with the weak 4f−π interactions.

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Nanostructuring of Rare‐earth‐based Single‐Molecule Magnets as Long‐range Ordered Arrays in the Framework of Organic Metal Halide Perovskites

Chai

¹

,

Zhou

²

,

Hao

³

et al. 2023

Angewandte Chemie

0

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The nanostructuring of single‐molecule magnets (SMMs) on substrates, in nanotubes and periodic frameworks is highly desired for the future magnetic recording devices. However, the ability to organize SMMs into long‐range ordered arrays in these systems is still lacking. Here, we report the incorporation of magnetic (RECl2(H2O)6)+ (RE=rare earths) molecular groups into the framework of an organic metal halide perovskite (OMHP)—(H2dabco)CsCl3. Intriguingly, we show the incorporated rare‐earth groups self‐organized into long‐range ordered arrays that uniformly and periodically distributed in the A sites of OMHP. The ordered (RECl2(H2O)6)+ groups serve as SMMs in the perovskite frameworks, exhibiting large effective magnetic moment, moderate magnetic anisotropy and two‐step relaxation behavior. With the additional merit of great structural flexibility and multifunction of OMHPs, the preparation of the first SMMs@OMHP magnetic materials furthers the development of molecular spintronics.

show abstract

Nanostructuring of Rare‐earth‐based Single‐Molecule Magnets as Long‐range Ordered Arrays in the Framework of Organic Metal Halide Perovskites

Chai

¹

,

Zhou

²

,

Hao

³

et al. 2023

View full text Add to dashboard Cite

The nanostructuring of single‐molecule magnets (SMMs) on substrates, in nanotubes and periodic frameworks is highly desired for the future magnetic recording devices. However, the ability to organize SMMs into long‐range ordered arrays in these systems is still lacking. Here, we report the incorporation of magnetic (RECl2(H2O)6)+ (RE=rare earths) molecular groups into the framework of an organic metal halide perovskite (OMHP)—(H2dabco)CsCl3. Intriguingly, we show the incorporated rare‐earth groups self‐organized into long‐range ordered arrays that uniformly and periodically distributed in the A sites of OMHP. The ordered (RECl2(H2O)6)+ groups serve as SMMs in the perovskite frameworks, exhibiting large effective magnetic moment, moderate magnetic anisotropy and two‐step relaxation behavior. With the additional merit of great structural flexibility and multifunction of OMHPs, the preparation of the first SMMs@OMHP magnetic materials furthers the development of molecular spintronics.

show abstract

Electro‐Conductive Single‐Molecule Magnet Composed of a Dysprosium(III)‐Phthalocyaninato Double‐Decker Complex with Magnetoresistance

Cited by 3 publications

References 49 publications

4f−π Molecular Hybrid Exhibiting Rich Conductive Phases and Slow Relaxation of Magnetization

4f−π Molecular Hybrid Exhibiting Rich Conductive Phases and Slow Relaxation of Magnetization

Nanostructuring of Rare‐earth‐based Single‐Molecule Magnets as Long‐range Ordered Arrays in the Framework of Organic Metal Halide Perovskites

Nanostructuring of Rare‐earth‐based Single‐Molecule Magnets as Long‐range Ordered Arrays in the Framework of Organic Metal Halide Perovskites

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