Three‐Dimensional Chiral Molecule‐Based Ferrimagnet with Triple‐Helical‐Strand Structure

Imai, Hiroyuki; Inoue, Kazuhide; Kikuchi, Kazuki; Yoshida, Yusuke; Ito, Mitsuhiro; Sunahara, Tetsuya; Onaka, Satoru

doi:10.1002/ange.200460867

Cited by 20 publications

(7 citation statements)

References 30 publications

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“…[17] Several optically active magnets have been reported over the years. A variety of chiral building blocks have been used to impose chirality into the magnetic networks, including chiral capping ligands, [18] chiral organic radicals, [19] and chiral metal complexes.…”

Section: Introductionmentioning

confidence: 99%

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = Mn^II, Fe^II, Co^II, Ni^II; L‐tart = (2R,3R)‐(+)‐tartrate)

Coronado

Galán‐Mascarós

Gómez‐García

et al. 2006

Chemistry A European J

120

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A new series of layered magnets with the formula [M(L-tartrate)] (M = Mn(II), Co(II), Fe(II), Ni(II); L-tartrate = (2R,3R)-(+)-tartrate) has been prepared. All of these compounds are isostructural and crystallize in the chiral orthorhombic space group I222, as found by X-ray structure analysis. Their structure consists of a three-dimensional polymeric network in which each metal shows distorted octahedral coordination bound to four L-tartrate ligands, two of which chelate through an alcohol and a carboxylate group and the other two bind terminally through a monodentate carboxylate group. The chirality of the ligand imposes a Delta conformation on all metal centers. Magnetically, the paramagnetic metal centers form pseudotetragonal layers in which each metal is surrounded by four other metals, with syn,anti carboxylate bridges. These salts show intralayer antiferromagnetic or ferromagnetic interactions, depending on the electronic configuration of the metal, and weak interlayer antiferromagnetic interaction. In all cases the magnetic properties are strongly affected by the anisotropy of the system, and the presence of magnetic canting has been found. The Mn derivative behaves as a weak ferromagnet with a critical temperature of 3.3 K. The Ni derivative shows very unusual magnetic behavior in that it exhibits antiferromagnetic ordering below 6 K, the onset of spontaneous magnetization arising from spin reorientation into a canted phase below 4.5 K, and a field-induced ferromagnetic state above 0.3 T at 2 K, behavior typical of metamagnets. The Fe and Co derivatives show antiferromagnetic interactions between spin carriers, but do not order above 2 K.

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Section: Introductionmentioning

confidence: 99%

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = Mn^II, Fe^II, Co^II, Ni^II; L‐tart = (2R,3R)‐(+)‐tartrate)

Coronado

Galán‐Mascarós

Gómez‐García

et al. 2006

Chemistry A European J

120

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“…The reaction mixture was allowed to cool to room temperature and stirred for 30 min. After removal of the solvent (rotary evaporator, 40 8C), the deep green residue was treated repeatedly (6 ) with methanol (12 mL), which was removed by evaporation. The crude reaction product was suspended in methanol (12 mL), and the turquoise powder was filtered off.…”

Section: Methodsmentioning

confidence: 99%

“…[5] In the last case, it is an interesting challenge to create chiral magnets, presenting at the same time magnetic circular dichroism (Faraday effect), natural circular dichroism (Cotton effect), and therefore possible cross-effects. [6] One synthetic approach, leading to these chiral supramolecular architectures, is the combination of suitably designed enantiomerically pure organic ligands and metal ions, [7] which we used earlier for the diastereoselective synthesis of copper(II) cubanes. [8] Abstract: Enantiomerically pure, vicinal diols 1 afforded in a two-step synthesis (etherification and subsequent Claisen condensation) chiral bis-1,3-diketones H 2 L (S,S) (3 a-c) with different substitution patterns.…”

Section: Introductionmentioning

confidence: 99%

Enantiospecific Syntheses of Copper Cubanes, Double‐Stranded Copper/Palladium Helicates, and a (Dilithium)–Dinickel Coronate from Enantiomerically Pure Bis‐1,3‐diketones—Solid‐State Self‐Organization Towards Wirelike Copper/Palladium Strands

Saalfrank

Spitzlei

Scheurer

et al. 2008

Chemistry A European J

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Enantiomerically pure, vicinal diols 1 afforded in a two-step synthesis (etherification and subsequent Claisen condensation) chiral bis-1,3-diketones H(2)L((S,S)) (3 a-c) with different substitution patterns. Reaction of these C(2)-symmetric ligands with various transition-metal acetates in the presence of alkali ions generated distinct polynuclear aggregates 4-8 by diastereoselective self-assembly. Starting from copper(II) acetate monohydrate and depending on the ratio of transition-metal ion to alkali ion to ligand, chiral tetranuclear copper(II) cubanes (C,C,C,C)-[Cu(4)(L((S,S)))(2)(OMe)(4)] (4 a-c) or dinuclear copper(II) helicates (P)-[Cu(2)(L((S,S)))(2)] (5) could be synthesized with square-pyramidal and square-planar coordination geometry at the metal center. In analogy to the last case, with palladium(II) acetate double-stranded helical systems (P)-[Pd(2)(L((S,S)))(2)] (6,7) were accessible exhibiting a linear self-organization of ligand-isolated palladium filaments in the solid state with short inter- and intramolecular metal distances. Finally, the introduction of hexacoordinate nickel(II) in combination with lithium hydroxide monohydrate and chiral ligand H(2)L((S,S)) (3 a) allowed the isolation of enantiomerically pure dinuclear nickel(II) coronate [(LiMeOH)(2) subset{(Delta,Lambda)-Ni(2)(L((S,S)))(2)(OMe)(2)}] (8) with two lithium ions in the voids, defined by the oxygen donors in the ligand backbone. The high diastereoselectivity, induced by the chiral ligands, during the self-assembly process in the systems 4-8 could be exemplarily proven by circular dichroism spectroscopy for the synthesized enantiomers of the chiral copper(II) cubane 4 a and palladium(II) helicate 6.

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“…[9,10] For that reason, the synthesis of chiral, enantiomerically pure singlemolecule magnets is of special interest (e.g. for magnetodichroism [11] ), and complexes like cubane 7 and ent-7 are potential candidates.…”

Section: àmentioning

confidence: 99%

Enantiomerically Pure Copper(II) Cubanes [Cu₄L₂(OMe)₄] from Chiral Bis‐1,3‐diketones H₂L through Diastereoselective Self‐Assembly

et al. 2005

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Three‐Dimensional Chiral Molecule‐Based Ferrimagnet with Triple‐Helical‐Strand Structure

Cited by 20 publications

References 30 publications

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = Mn^II, Fe^II, Co^II, Ni^II; L‐tart = (2R,3R)‐(+)‐tartrate)

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = Mn^II, Fe^II, Co^II, Ni^II; L‐tart = (2R,3R)‐(+)‐tartrate)

Enantiospecific Syntheses of Copper Cubanes, Double‐Stranded Copper/Palladium Helicates, and a (Dilithium)–Dinickel Coronate from Enantiomerically Pure Bis‐1,3‐diketones—Solid‐State Self‐Organization Towards Wirelike Copper/Palladium Strands

Enantiomerically Pure Copper(II) Cubanes [Cu₄L₂(OMe)₄] from Chiral Bis‐1,3‐diketones H₂L through Diastereoselective Self‐Assembly

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Three‐Dimensional Chiral Molecule‐Based Ferrimagnet with Triple‐Helical‐Strand Structure

Cited by 20 publications

References 30 publications

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = MnII, FeII, CoII, NiII; L‐tart = (2R,3R)‐(+)‐tartrate)

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = MnII, FeII, CoII, NiII; L‐tart = (2R,3R)‐(+)‐tartrate)

Enantiospecific Syntheses of Copper Cubanes, Double‐Stranded Copper/Palladium Helicates, and a (Dilithium)–Dinickel Coronate from Enantiomerically Pure Bis‐1,3‐diketones—Solid‐State Self‐Organization Towards Wirelike Copper/Palladium Strands

Enantiomerically Pure Copper(II) Cubanes [Cu4L2(OMe)4] from Chiral Bis‐1,3‐diketones H2L through Diastereoselective Self‐Assembly

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Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = Mn^II, Fe^II, Co^II, Ni^II; L‐tart = (2R,3R)‐(+)‐tartrate)

Chiral Molecular Magnets: Synthesis, Structure, and Magnetic Behavior of the Series [M(L‐tart)] (M = Mn^II, Fe^II, Co^II, Ni^II; L‐tart = (2R,3R)‐(+)‐tartrate)

Enantiomerically Pure Copper(II) Cubanes [Cu₄L₂(OMe)₄] from Chiral Bis‐1,3‐diketones H₂L through Diastereoselective Self‐Assembly