Three Phases of [Fe(C5Me5)2]+[TCNQ]-: Ferromagnetism in a New Structural Phase

Broderick, William E.; Eichhorn, David M.; Liu, Xiaohua; Toscano, Paul M.; Owens, Scott M.; Hoffman, Brian M.

doi:10.1021/ja00117a045

Cited by 60 publications

(49 citation statements)

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“…• C resulted in a bulk 3D ferromagnet where T C = 3.1 K [9]. The chemistry of these systems is incredibly rich where there can be strong solvent dependencies of Fe-Fe intrachain distances, which effects the magnetism [10,11].…”

Section: Introductionmentioning

confidence: 99%

Separating the ferromagnetic and glassy behavior within the metal-organic magnetNi(TCNQ)2

et al. 2015

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Publisher's copyright statement:Reprinted with permission from the American Physical Society: Physical Review B 92, 184431 c 2015 by the American Physical Society. Readers may view, browse, and/or download material for temporary copying purposes only, provided these uses are for noncommercial personal purposes. Except as provided by law, this material may not be further reproduced, distributed, transmitted, modied, adapted, performed, displayed, published, or sold in whole or part, without prior written permission from the American Physical Society.Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. An in-depth study of the metal-organic magnet Ni(TCNQ) 2 was conducted where the deuterated form was synthesised both to attempt to alter the magnetic properties of the material and to be advantageous in techniques such as neutron scattering and muon spectroscopy. Deuteration saw a 3 K increase in T C with magnetization and heat capacity measurements demonstrating a spin wave contribution at low temperatures confirming the 3D nature of the ferromagnetic state shown by Ni(TCNQ − D 4 ) 2 . AC susceptibility results suggest there is a glassy component associated with the magnetically ordered state, though muon spectroscopy measurements did not support the presence of a spin glass state. Instead muon spectroscopy at zero magnetic field indicated the presence of two magnetic transitions, one at 20 K and another below 6 K; the latter is likely due to the system entering a quasistatic regime, similar to what one might expect of a superspin or cluster glass. Neutron diffraction measurements further supported this by revealing very weak magnetic Bragg peaks suggesting that the magnetism may have a short coherence length and be confined to small grains or clusters. The separation of the ferromagnetic and glassy magnetic components of the material's properties suggest that this system may show promise as a metal-organic magnet which is easily modified to change its magnetic properties, providing larger grain sizes can be synthesized.

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Section: Introductionmentioning

confidence: 99%

Separating the ferromagnetic and glassy behavior within the metal-organic magnetNi(TCNQ)2

et al. 2015

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“…[10] Another derivative, of formula [Fe(C 5 Me 5 ) 2 ][TCNQ] 2 , is conducting and shows a one-dimensional stack of acceptors. [11] This variety of structural motifs and properties shows how subtle changes in electronic density or in the interionic interactions can influence the bulk properties of the material.…”

Section: ][Tcne]mentioning

confidence: 99%

Radical Ion Salts Obtained from Substituted Ferrocene Cations and the Organic Acceptor TCNQ − Synthesis, Structure and Physical Properties

et al. 2003

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The compounds [Fe(C5H5)(C5H4CH2NMe3)][TCNQ] (1), [Fe(C5H5)(C5H4CH2NMe3)][TCNQ]2.MeCN (2) and [Fe(C5H5)(C5H4CH=CH‐p‐C5H4NMe)][TCNQ] (3) have been obtained from reaction of the corresponding ferrocene iodide and TCNQ or LiTCNQ. Their crystal structures have been determined, showing that 1 and 3 have only mononegative TCNQ radicals forming one‐dimensional stacks. In compound 3 the pyridine substituent also overlaps with the stacked TCNQ. The formation reaction of 2 implies the reduction of neutral TCNQ by the iodide anion; in this reaction the reduction is partial and the formal charge of every TCNQ is approximately 0.5 e− with some degree of electron delocalization. The TCNQs also overlap to form a one‐dimensional stack in the solid. The three compounds are diamagnetic, indicating a strong antiferromagnetic coupling between the TCNQ spins. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…Magnetic ordering does not occur above 2 K for 3a (y = ±3 K), however, a transition to an antiferromagnetic state occurs at a T c of 2.55 K (y = 3 K) for 3b, [6] and a transition to a ferromagnetic state occurs at a T c of 3.0 K for 3b (y = +3.8 K). [7] The ferromagnetic behavior in 3g is attributed to 4-Nitophenyl nitronyl nitroxide, 4, is a more complex system, as four deep-green polymorphs (Fig. 4), each with differing magnetic properties, have been reported.…”

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confidence: 98%

“…In addition to this kinetic phase, upon slow cooling a thermodynamic phase possessing parallel _DADADA_ one-dimensional chains forms. [6,7] Slow cooling in acetonitrile to room temperature leads to the isolation of the green triclinic, metamagnetic phase (3b) (Fig. 3b), [6] while cooling to ±20 C leads to the monoclinic, ferromagnetic phase (purple parallelepipeds) (3g) (Fig.…”

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Polymorphic Molecular Materials—The Importance of Tertiary Structures

Miller¹

1998

Adv. Mater.

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Molecule‐based materials can exhibit a variety of technologically useful cooperative properties not associated with individual molecules, such as ferromagnetism, superconductivity, and ferroelectricity. Selected examples are used to illustrate the fact that, although in general the molecular structure differs in only minor ways, the qualitative or quantitative differences of the crystal or tertiary structure may lead to substantial differences in the solid‐state bulk (magnetic) properties, e.g., presence or lack of ordering, or simply a raising or lowering of the ordering temperature.

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Three Phases of [Fe(C5Me5)2]+[TCNQ]-: Ferromagnetism in a New Structural Phase

Cited by 60 publications

References 1 publication

Separating the ferromagnetic and glassy behavior within the metal-organic magnetNi(TCNQ)2

Separating the ferromagnetic and glassy behavior within the metal-organic magnetNi(TCNQ)2

Radical Ion Salts Obtained from Substituted Ferrocene Cations and the Organic Acceptor TCNQ − Synthesis, Structure and Physical Properties

Polymorphic Molecular Materials—The Importance of Tertiary Structures

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