Spin dynamics of the charge-transfer phase transition of an iron mixed-valence complex observed using muon spin relaxation spectroscopy

Kida, Noriyuki; Enomoto, Masaya; Watanabe, Isao; Suzuki, Takao; Kojima, Naoya

doi:10.1103/physrevb.77.144427

Cited by 11 publications

(18 citation statements)

References 20 publications

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“…The Mn II -substituted complexes with the low x values of 0.00 ≤ x ≤ 0.04 exhibit the CT phase in the temperature range between T ↑ (CT) and T ↓ (CT). In this region, the CTPT raises the dynamic oscillation between Fe II and Fe III , which is found by µSR measurement [58,59]. Below T ↓ (CT), the paramagnetic phase for the complexes with 0.00 < x ≤ 0.04, which is denoted as P mix in Figure 10, becomes the mixing state between the LTP and HTP as a result of the partial suppression of the CTPT.…”

Section: Discussionmentioning

confidence: 78%

Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (n-C3H7)4N[FeII1−xMnIIxFeIII(dto)3]

et al. 2018

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The dithiooxalato-bridged iron mixed-valence complex (n-C3H7)4N[FeIIFeIII(dto)3] (dto = dithiooxalato) undergoes a novel charge-transfer phase transition (CTPT) accompanied by electron transfer between adjacent FeII and FeIII sites. The CTPT influences the ferromagnetic transition temperature according to the change of spin configuration on the iron sites. To reveal the mechanism of the CTPT, we have synthesized the series of metal-substituted complexes (n-C3H7)4N[FeII1-xMnIIxFeIII(dto)3] (x = 0–1) and investigated their physical properties by means of magnetic susceptibility and dielectric constant measurements. With increasing MnII concentration, x, MnII-substituted complexes show the disappearance of CTPT above x = 0.04, while the ferromagnetic phase remains in the whole range of x. These results are quite different from the physical properties of the ZnII-substituted complex, (n-C3H7)4N[FeII1-xZnIIxFeIII(dto)3], which is attributed to the difference of ion radius as well as the spin states of MnII and ZnII.

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Section: Discussionmentioning

confidence: 78%

Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (n-C3H7)4N[FeII1−xMnIIxFeIII(dto)3]

et al. 2018

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“…Figure 14 shows the ZF-μSR time spectra of n = 3 between 1.9 and 200 K [ 41 ]. A Gaussian-type depolarization behavior of the time spectrum is observed at 200 K. The time spectrum changes to an exponential type with decreasing temperature below 30 K, and a loss of the initial asymmetry is observed below 20 K. Within a time region longer than 1 μs, the time spectrum slightly recovers with decreasing temperature down to 1.9 K. This series of behaviors is a sign of the appearance of the ferromagnetically ordered state ( T C = 7 K).…”

Section: A[fe II Fe Iii (Dtomentioning

confidence: 99%

“…In particular, organic-inorganic hybrid systems such as layered double hydroxides (LDHs) [20,21,22,23,24], oxalato-bridged bimetal complexes A[M II M’ III (ox) 3 ] (A = cation, M, M’ = metal, ox = C 2 O 4 ) [25,26,27,28,29,30], dithiooxalato-bridged bimetal complexes A[M II M’ III (dto) 3 ] (A = cation, M, M’ = metal, dto = C 2 S 2 O 2 ) [31,32,33,34,35,36,37,38,39,40,41,42], perovskite-type metal halides A 2 M II X 4 (A = cation, M = metal, X = halogen) [43,44,45], magnetic vesicles [46,47,48,49], or magnetic thin films [50,51,52] provide an excellent opportunity to control their magnetic properties by the intercalation of various molecules.…”

Section: Introductionmentioning

confidence: 99%

“…At the CTPT, we have found the iron valence fluctuation with a frequency of about 0.1 MHz by means of muon spin relaxation [41]. ( n -C n H 2n+1 ) 4 N[Fe II Fe III (dto) 3 ] (n = 3–6) undergo the ferromagnetic phase transitions [40].…”

Section: Introductionmentioning

confidence: 99%

“…In the case of ( n -C n H 2n+1 ) 4 N[Fe II Fe III (dto) 3 ], we have discovered a new type of phase transition called charge transfer phase transition (CTPT) where the thermally induced charge transfer between Fe II and Fe III occurs reversibly [ 33 , 34 ]. At the CTPT, we have found the iron valence fluctuation with a frequency of about 0.1 MHz by means of muon spin relaxation [ 41 ]. ( n -C n H 2n+1 ) 4 N[Fe II Fe III (dto) 3 ] (n = 3–6) undergo the ferromagnetic phase transitions [ 40 ].…”

Section: Introductionmentioning

confidence: 99%

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Progress of Multi Functional Properties of Organic-Inorganic Hybrid System, A[FeIIFeIIIX3] (A = (n-CnH2n+1)4N, Spiropyran; X = C2O2S2, C2OS3, C2O3S)

et al. 2010

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In the case of mixed-valence systems whose spin states are situated in the spin crossover region, new types of conjugated phenomena coupled with spin and charge are expected. From this viewpoint, we have investigated the multifunctional properties coupled with spin, charge and photon for the organic-inorganic hybrid system, A[FeIIFeIIIX3](A = (n-CnH2n+1)4N, spiropyran; X = dto(C2O2S2), tto(C2OS3), mto(C2O3S)). A[FeIIFeIII(dto)3] and A[FeIIFeIII(tto)3] undergo the ferromagnetic phase transitions, while A[FeIIFeIII(mto)3] undergoes a ferrimagnetic transition. In (n-CnH2n+1)4N [FeIIFeIII(dto)3](n = 3,4), a new type of phase transition called charge transfer phase transition (CTPT) takes place around 120 K, where the thermally induced charge transfer between FeII and FeIII occurs reversibly. At the CTPT, the iron valence state dynamically fluctuated with a frequency of about 0.1 MHz, which was confirmed by means of muon spin relaxation. The charge transfer phase transition and the ferromagnetic transition for (n-CnH2n+1)4N[FeIIFeIII(dto)3] remarkably depend on the size of intercalated cation. In the case of (SP)[FeIIFeIII(dto)3](SP = spiropyran), the photoinduced isomerization of SP under UV irradiation induces the charge transfer phase transition in the [FeIIFeIII(dto)3] layer and the remarkable change of the ferromagnetic transition temperature. In the case of (n-CnH2n+1)4N[FeIIFeIII(mto)3](mto = C2O3S), a rapid spin equilibrium between the high-spin state (S = 5/2) and the low-spin state (S = 1/2) at the FeIIIO3S3 site takes place in a wide temperature range, which induces the valence fluctuation of the FeS3O3 and FeO6 sites through the ferromagnetic coupling between the low spin state (S = 1/2) of the FeIIIS3O3 site and the high spin state (S = 2) of the FeIIO6 site.

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Molecular Magnetism of Metal Complexes and Light-Induced Phase Transitions

Kojima

Okazawa

2021

Topics in Applied Physics

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Spin dynamics of the charge-transfer phase transition of an iron mixed-valence complex observed using muon spin relaxation spectroscopy

Cited by 11 publications

References 20 publications

Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (n-C3H7)4N[FeII1−xMnIIxFeIII(dto)3]

Effect of Transition Metal Substitution on the Charge-Transfer Phase Transition and Ferromagnetism of Dithiooxalato-Bridged Hetero Metal Complexes, (n-C3H7)4N[FeII1−xMnIIxFeIII(dto)3]

Progress of Multi Functional Properties of Organic-Inorganic Hybrid System, A[FeIIFeIIIX3] (A = (n-CnH2n+1)4N, Spiropyran; X = C2O2S2, C2OS3, C2O3S)

Molecular Magnetism of Metal Complexes and Light-Induced Phase Transitions

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