Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra

Kitazawa, Takio; Kishida, Takuya; Kawasaki, Takeshi; Takahashi, Miwa

doi:10.1007/s10751-017-1436-4

Cited by 9 publications

(6 citation statements)

References 25 publications

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“…To investigate the SCO phenomenon, 57 Fe Mössbauer spectroscopy can be successfully used owing to its sensitivity to the valence, spin state, and coordination environment. Thus, numerous Fe-type, Hofmann-type complexes have been investigated using this spectroscopic technique. − Following the first report on the Mössbauer effect of 191 Ir in 1958 by Mössbauer, Pound described in 1959 that effect in 57 Fe for the first time . Recently, we have investigated a Hofmann-type complex bearing a pyrimidine-type ligand, i.e., {Fe(4-methylpyrimidine) 2 [Au(CN) 2 ] 2 } ( 1Au ) .…”

Section: Introductionmentioning

confidence: 99%

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)₂[Ag(CN)₂]₂}

2021

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The spin-crossover (SCO) phenomenon is an active area of research. This paper describes the synthesis of an Fe−Ag Hofmann-type complex, {Fe(4methylpyrimidine) 2 [Ag(CN) 2 ] 2 }, which demonstrates a one-step SCO and single-layer Hofmann-type structure with Ag−N interactions and no Ag−Ag interactions, which is strikingly different from the previously synthesized complex {Fe(4-methylpyrimidine) 2 [Au-(CN) 2 ] 2 } that contains Au−Au interactions and no Au−N interactions. This difference can be explained in terms of the lack of relativistic effect in the Ag atoms and the different cooperative effects caused by their different structures. A scan-rate-dependent hysteresis is observed using magnetic measurement whereas not using 57 Fe Mossbauer spectroscopy, suggesting that the spin transition is relatively slow.

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Section: Introductionmentioning

confidence: 99%

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)₂[Ag(CN)₂]₂}

2021

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“…The SCO phenomena can be explored by various magnetic and spectroscopic techniques including magnetic susceptibility measurement, Mössbauer spectroscopy [28,29], optical absorption and X-ray absorption spectroscopy (XAS) [4,30,31]. In those experimental techniques, external stimuli are applied to the specimen in order to observe the responses related to the spin states.…”

Section: Introductionmentioning

confidence: 99%

Soft X-ray Absorption Spectroscopy Study of Spin Crossover Fe-Compounds: Persistent High Spin Configurations under Soft X-ray Irradiation

et al. 2018

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Metal-organic complex exhibiting spin crossover (SCO) behavior has drawn attention for its functionality as a nanoscale spin switch. The spin states in the metal ions can be tuned by external stimuli such as temperature or light. This article demonstrates a soft X-ray–induced excited spin state trapping (SOXEISST) effect in Hofmann-like SCO coordination polymers of FeII(4-methylpyrimidine)2[Au(CN)2]2 and FeII(pyridine)2[Ni(CN)4]. A soft X-ray absorption spectroscopy (XAS) study on these polymers showed that the high spin configuration (HS; S = 2) was prevalent in Fe2+ ions during the measurement even at temperatures much lower than the critical temperatures (>170 K), manifesting HS trapping due to the X-ray irradiation. This is in strong contrast to the normal SCO behavior observed in FeII(1,10-phenanthroline)2(NCS)2, implying that the structure of the ligand chains in the polymers with relatively loose Fe-N coordination might allow a structural adaptation to stabilize the metastable HS state under the soft X-ray irradiation.

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“…For example, the transition in 3 occurs at T ↑ = 283 K and T ↓ = 269 K. This makes this complex interesting for near room temperature experiments and applications. Moreover, while in pyridine analogs the spin transition occurs at low temperatures, these new examples show that 2D analogs of Hofmann clathrates also may have spin transitions at temperatures close to those of their 3D analogs …”

Section: Resultsmentioning

confidence: 79%

Pyridazine‐Supported Polymeric Cyanometallates with Spin Transitions

et al. 2019

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Heterometallic cyano‐bridged spin‐crossover complexes form a large family of switchable compounds with different structural motives and diverse transition characteristics. Here we report on the hysteretic water‐dependent spin transitions found in the family of [Fe(pyridazine)2M(CN)4] frameworks (M = Ni, Pd, Pt). The structure of three new spin‐crossover compounds is built of cyanometallic layers supported by pyridazine ligands. The frameworks contain water guest molecules that can be removed upon heating. Spin transition was found in both hydrated and dehydrated compounds, while the removal of water stimulated a complete spin state switch. Mössbauer spectroscopy revealed two different high‐spin centers in hydrated frameworks, and only one of them is switchable. The compounds display a pronounceable thermochromism, changing their color from red in low‐spin to yellow in high‐spin. The work shows a perspective of 1,2‐diazine application for the design of switchable complexes.

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Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra

Cited by 9 publications

References 25 publications

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)₂[Ag(CN)₂]₂}

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)₂[Ag(CN)₂]₂}

Soft X-ray Absorption Spectroscopy Study of Spin Crossover Fe-Compounds: Persistent High Spin Configurations under Soft X-ray Irradiation

Pyridazine‐Supported Polymeric Cyanometallates with Spin Transitions

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Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra

Cited by 9 publications

References 25 publications

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)2[Ag(CN)2]2}

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)2[Ag(CN)2]2}

Soft X-ray Absorption Spectroscopy Study of Spin Crossover Fe-Compounds: Persistent High Spin Configurations under Soft X-ray Irradiation

Pyridazine‐Supported Polymeric Cyanometallates with Spin Transitions

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Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)₂[Ag(CN)₂]₂}

Effects of Both Methyl and Pyrimidine Groups in Fe–Ag Spin-Crossover Hofmann-Type Complex {Fe(4-Methylpyrimidine)₂[Ag(CN)₂]₂}