Transformation between Monovalent and Divalent Ionic Solids: An Ionic(I)–Ionic(II) Phase Transition in a Biferrocene–F<sub>1</sub>TCNQ Charge-Transfer Complex

Mochida, Tomoyuki; Takazawa, Kousuke; Takahashi, Miwa; Takeda, M.; Nishio, Y.; Sato, Michiko; Kajita, Kôji; Mori, H.; Matsushita, Michio M.; Sugawara, Tadashi

doi:10.1143/jpsj.74.2214

Cited by 33 publications

(13 citation statements)

References 14 publications

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“…Upon cooling to around 120 K, charge transfer from npbifc + to (F 1 ‐tcnq) 3 − is induced to form npbifc 2+ and (F 1 ‐tcnq) 3 2− . The change in the redox state is illustrated in Figure 14 a 104. Calorimetric studies revealed that the transition entropy is 20±2 J mol −1 K −1 .…”

Section: Other Charge‐transfer Systemsmentioning

confidence: 97%

“…More recently, a transformation between the monovalent state D + A 3 − and the divalent state D 2+ A 3 2− was observed in [(npbifc)(F 1 ‐tcnq) 3 ] (npbifc=dineopentylbisferrocene; F 1 ‐tcnq=fluorotetracyanoquinodimethane) 104. 105 At room temperature, this compound is a monovalent solid with the monocation npbifc + and the trimer monoanion (F 1 ‐tcnq) 3 − .…”

Section: Other Charge‐transfer Systemsmentioning

confidence: 99%

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Control of Magnetic Properties through External Stimuli

Sato¹,

Tao²,

Zhang³

2007

Angew Chem Int Ed

1,071

615

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The magnetic properties of many magnetic materials can be controlled by external stimuli. The principal focus here is on the thermal, photochemical, electrochemical, and chemical control of phase transitions that involve changes in magnetization. The molecular compounds described herein range from metal complexes, through pure organic compounds to composite materials. Most of the Review is devoted to the properties of valence-tautomeric compounds, molecular magnets, and spin-crossover complexes, which could find future application in memory devices or optical switches.

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Section: Other Charge‐transfer Systemsmentioning

confidence: 97%

Section: Other Charge‐transfer Systemsmentioning

confidence: 99%

Control of Magnetic Properties through External Stimuli

Sato¹,

Tao²,

Zhang³

2007

Angew Chem Int Ed

1,071

615

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show abstract

“…Die ungepaarten Spins der isolierten TTF(D 1+ )-und CA(A 1À )-Einheiten an den Domänengrenzen führen zu den experimentell beobachteten ESR-Signalen. [104,105] Bei Raumtemperatur handelt es sich um einen einwertigen Festkörper mit dem Monokation npbifc + und Abbildung 13. a) Phasenumwandlung neutral ! [97] Nochmals wird darauf hingewiesen, dass die neutrale und die ionische Phase diamagnetisch sind, sodass TTF-CA und verwandte Verbindungen weniger wegen ihrer magnetischen als vielmehr wegen ihrer dielektrischen Eigenschaften interessant sind.…”

Section: üBergänge Zwischen Neutralen Und Ionischen Zuständen Und Verunclassified

“…Bei Abkühlung auf ca. [104] In kalorimetrischen Messungen wurde eine Übergangsentropie von (20 AE 2) J mol À1 K À1 ermittelt. Die ¾nderung des Redoxzustandes ist in Abbildung 14 dargestellt.…”

Section: Steuerung Magnetischer Eigenschaftenunclassified

Magnetische Molekülverbindungen: Schaltung magnetischer Eigenschaften durch externe Stimuli

2007

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Man kennt eine Vielzahl magnetischer Materialien, deren magnetische Eigenschaften durch externe Stimuli geschaltet werden können. Das Hauptaugenmerk liegt auf der thermischen, photochemischen, elektrochemischen und chemischen Steuerung von Phasenübergängen, die mit einem Wechsel der Magnetisierung einhergehen. Die Bandbreite der beschriebenen Spezies reicht von Metallkomplexen über rein organische Verbindungen bis zu Kompositmaterialien, wobei der Schwerpunkt dieses Aufsatzes auf den Eigenschaften von valenztautomeren Verbindungen, molekularen Magneten und Spin‐Crossover‐Komplexen liegt, für die Anwendungen als Speichermedien oder optische Schalter in Aussicht stehen.

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“…Furthermore, the cation exhibited the valence‐trapped structure. The average Fe–Cp (centroid) distances of Fe1 ( 8 : 1.66 Å, 9 : 1.65 Å; Table 1) closely resembled the distances in neutral ferrocene, and those of Fe2 ( 8 : 1.71 Å, 9 : 1.72 Å) closely resembled the distances in the ferrocenium cation 10a. This charge localization was attributed to the electron‐withdrawing effect of the bromo substituent, which destabilized the cationic charge of Fe1.…”

Section: Resultsmentioning

confidence: 70%

Mixed‐Valence Biferrocenium Salts of X_n–TCNQ (X = F, Cl; n = 1, 2): Correlation between Molecular Structures and Assembled Structures

et al. 2014

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Charge‐transfer salts composed of biferrocene derivatives and Xn–TCNQ (X = F, Cl; n = 1, 2; TCNQ = tetracyanoquinodimethane) were prepared and crystallographically characterized. All nine salts exhibited a 1:2 donor/acceptor (D/A) ratio consisting of mixed‐valence biferrocenium cations and anions with acceptor dimers. The packing patterns were correlated to the donor substituents. On the basis of the π–π interactions of the cations, the observed structures were classified into three categories: segregated‐stack structures for the biferrocenium and dibromo‐biferrocenium salts, mixed‐stack structures [···(DA2)n···] for the diiodo‐biferrocenium salts, and intermediate structures [···(DDA2A2)n···] for the bromo‐biferrocenium salts.

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Transformation between Monovalent and Divalent Ionic Solids: An Ionic(I)–Ionic(II) Phase Transition in a Biferrocene–F₁TCNQ Charge-Transfer Complex

Cited by 33 publications

References 14 publications

Control of Magnetic Properties through External Stimuli

Control of Magnetic Properties through External Stimuli

Magnetische Molekülverbindungen: Schaltung magnetischer Eigenschaften durch externe Stimuli

Mixed‐Valence Biferrocenium Salts of X_n–TCNQ (X = F, Cl; n = 1, 2): Correlation between Molecular Structures and Assembled Structures

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Transformation between Monovalent and Divalent Ionic Solids: An Ionic(I)–Ionic(II) Phase Transition in a Biferrocene–F1TCNQ Charge-Transfer Complex

Cited by 33 publications

References 14 publications

Control of Magnetic Properties through External Stimuli

Control of Magnetic Properties through External Stimuli

Magnetische Molekülverbindungen: Schaltung magnetischer Eigenschaften durch externe Stimuli

Mixed‐Valence Biferrocenium Salts of Xn–TCNQ (X = F, Cl; n = 1, 2): Correlation between Molecular Structures and Assembled Structures

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Product

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Transformation between Monovalent and Divalent Ionic Solids: An Ionic(I)–Ionic(II) Phase Transition in a Biferrocene–F₁TCNQ Charge-Transfer Complex

Mixed‐Valence Biferrocenium Salts of X_n–TCNQ (X = F, Cl; n = 1, 2): Correlation between Molecular Structures and Assembled Structures