Humidity-induced magnetization and magnetic pole inversion in a cyano-bridged metal assembly

Ohkoshi, Shin‐ichi; Arai, Ken‐ichi; Sato, Yusuke; Hashimoto, Kazuhito

doi:10.1038/nmat1260

Cited by 343 publications

(212 citation statements)

References 18 publications

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“…For general background on Prussian blue compounds, see . For related literature, see: Egan et al (2006); Ferlay et al (1995); Gü del et al (1973); Gadet et al (1992); Hatlevik et al (1999); Holmes & Girolami (1999); Ludi et al (1970); Margadonna et al (2004); Ohkoshi & Hashimoto (2001); Ohkoshi et al (1997Ohkoshi et al ( , 2000Ohkoshi et al ( , 2004Ohkoshi et al ( , 2005; Sato et al (1996); Tokoro et al (2003Tokoro et al ( , 2004; Zeigler et al (1999).…”

Section: Related Literaturementioning

confidence: 99%

Poly[[hexa-μ-cyanido-manganese(II)iron(III)] pentahydrate]

et al. 2008

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Key indicators: single-crystal X-ray study; T = 90 K; mean (Mn-O) = 0.012 Å; Hatom completeness 1%; disorder in main residue; R factor = 0.047; wR factor = 0.136; data-to-parameter ratio = 13.2.The structure of the title compound, Mn II [Fe III (CN) 6 ] 2/3 Á-5H 2 O, features a face-centered cubic -Mn-NC-Fe-framework with both Mn and Fe having site symmetry m3m. Since one-third of the [Fe(CN) 6 ] 3À units are missing for a given formula in order to maintain charge neutrality, each Mn atom around such a vacancy is coordinated not only by the N atoms of the CN groups but also by the O atoms of the ligand water molecules. In addition to ligand water molecules, two types of non-coordinated water molecules, so-called zeolitic water molecules, exist in the interstitial sites of the -Mn-NC-Feframework. The positions of the O atoms of the zeolitic water molecules are fixed by the linkage via hydrogen bonds between ligand water and zeolitic water molecules. The structure is related to a recently reported rubidium manganese hexacyanoferrate. Site occupancy factors for Fe, C, N are 0.67; for two O atoms the value is 0.83 and for one O atom is 0.17. (1997, 2000, 2004, 2005); Sato et al. (1996);Tokoro et al. (2003Tokoro et al. ( , 2004Zeigler et al. (1999). Related literature ExperimentalCrystal data Mn[Fe(CN)

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Section: Related Literaturementioning

confidence: 99%

Poly[[hexa-μ-cyanido-manganese(II)iron(III)] pentahydrate]

et al. 2008

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“…This characteristic led us to prepare guest‐induced switching materials associated with the N–I phase transition, as reported for some porous coordination polymers (PCPs) in terms of spin states,23, 24, 25 electrical conductivity,26, 27 and magnetic ordering 28, 29, 30, 31, 32, 33, 34, 35…”

Section: Resultsmentioning

confidence: 88%

Magnetic Sponge with Neutral–Ionic Phase Transitions

et al. 2017

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Phase transitions caused by the charge instability between the neutral and ionic phases of compounds, i.e., N–I phase transitions, provide avenues for switching the intrinsic properties of compounds related to electron/spin correlation and dipole generation as well as charge distribution. However, it is extremely difficult to control the transition temperature (T c) for the N–I phase transition, and only chemical modification based on the original material have been investigated. Here, a design overview of the tuning of N–I phase transition by interstitial guest molecules is presented. This study reports a new chain coordination‐polymer [Ru2(3,4‐Cl2PhCO2)4TCNQ(EtO)2]∙DCE (1‐DCE; 3,4‐Cl2PhCO2 − = 3,4‐dichlorobenzoate; TCNQ(EtO)2 2,5‐diethoxy‐7,7,8,8‐tetracyanoquinodimethane; and DCE = 1,2‐dichloroethane) that exhibits a one‐step N–I transition at 230 K (= T c) with the N‐ and I‐states possessing a simple paramagnetic state and a ferrimagnetically correlated state for the high‐ and low‐temperature phases, respectively. The T c continuously decreases depending on the content of DCE, which eventually disappears with the complete evacuation of DCE, affording solvent‐free compound 1 with the N‐state in the entire temperature range (this behavior is reversible). This is an example of tuning the in situ T c for the N–I phase transition via the control of the interstitial guest molecules.

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“…The humidity sensitivity and the correlation among defect structure, conductivity, and magnetism suggests applications in H or moisture sensors, molecule detection, spintronics, photocatalysis, fuel cells, and other multifunctional materials. [40][41][42] …”

Section: Discussionmentioning

confidence: 99%

“…[36][37][38][39][40][41] Adsorption/desorption of hydroxyls produces the moment variation for our Ti oxide clusters. Adsorption/ desorption of water molecules give rise to the moment variation for molecular magnets.…”

Section: Summary Of Dft Calculationsmentioning

confidence: 96%

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Experimental and theoretical studies of hydroxyl-induced magnetism in TiO nanoclusters

et al. 2012

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A main challenge in understanding the defect ferromagnetism in dilute magnetic oxides is the direct experimental verification of the presence of a particular kind of defect and distinguishing its magnetic contributions from other defects. The magnetic effect of hydroxyls on TiO nanoclusters has been studied by measuring the evolution of the magnetic moment as a function of moisture exposure time, which increases the hydroxyl concentration. Our combined experiment and density-functional theory (DFT) calculations show that as dissociative water adsorption transforms oxygen vacancies into hydroxyls, the magnetic moment shows a significant increase. DFT calculations show that the magnetic moment created by hydroxyls arises from 3d orbitals of neighboring Ti sites predominantly from the top and second monolayers. The two nonequivalent hydroxyls contribute differently to the magnetic moment, which decreases as the separation of hydroxyls increases. This work illustrates the essential interplay among defect structure, local structural relaxation, charge redistribution, and magnetism. The microscopic differentiation and clarification of the specific roles of each kind of intrinsic defect is critical for the future applications of dilute magnetic oxides in spintronic or other multifunctional materials.

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Humidity-induced magnetization and magnetic pole inversion in a cyano-bridged metal assembly

Cited by 343 publications

References 18 publications

Poly[[hexa-μ-cyanido-manganese(II)iron(III)] pentahydrate]

Poly[[hexa-μ-cyanido-manganese(II)iron(III)] pentahydrate]

Magnetic Sponge with Neutral–Ionic Phase Transitions

Experimental and theoretical studies of hydroxyl-induced magnetism in TiO nanoclusters

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