Mixed‐Valence Electron Transfer of Cyanide‐Bridged Multimetallic Systems

Su, Shao‐Dong; Wu, Xintao; Sheng, Tianlu

doi:10.1002/9783527835287.ch8

Cited by 2 publications

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“…Considering that the stretching frequency of the cyanido group (CN – ) is characteristic in IR spectral and easily observed, especially because it can sensitively reflect the spin state of iron(II) complexes, CpMe n (dppe)Fe II CN ( n = 0, 1–5) is used to be the organometal fragment to synthesize the cyanido-bridged binuclear complexes Fe II L2- C N-Fe II L1 with [Fe II N 6 ] center. The N -terminal of the CN bridge is the spin transition site, and ligand field strength is regulated by modifying the L2 ligand at the C -terminal of the bridge to predict and regulate the SCO behavior.…”

Section: Introductionmentioning

confidence: 99%

Regulable Spin-Crossover Behaviors of a Family of Cyanido-Bridged Binuclear Iron(II) Compounds with a Thermally Induced Ultrafast High–Low Spin State Interconversion

Huang,

He,

Yang

et al. 2024

Crystal Growth & Design

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A family of five new cyanido-bridged binuclear Fe1 II -NC-Fe2 II complexes, [(PY 5 OMe)Fe II NCFe II (dppe)CpMe n ]-(OTf) 2 •CH 3 CN (CpMe n = alkyl cyclopentadienyl, n = 0 (1), 1 (2), 3 (3), 4 (4), 5 (5); dppe = 1, 2-bis(diphenylphosphino)ethane; PY 5 OMe = 2,6-bis((2-pyridyl)methoxymethane)pyridine; and OTf = CF 3 SO 3 −) have been synthesized and well characterized. Among them, Fe1 II located at the N-terminal of the cyano group is the spin transition site, and the C-terminal Fe2 II -fragment serves as an electron donor. Magnetic studies demonstrate that the electron-donating ability of the C-terminal substituents has a significant influence on the spin-state transition behavior of Fe1 II . The spin transition temperature (T 1/2 ) of the complexes can be regulated by the methyl number in the Cp ligand at the C-terminal. With the increase of the methyl substituents of the cyclopentadiene ligand, the spin transition area shifts toward a lower temperature. And this conclusion is also applicable to desolvated 1−5. Furthermore, a thermally induced ultrafast high−low spin interconversion (∼10 −12 s) around room temperature has been observed in complex 3, confirmed by IR and UV−vis−NIR spectra, the time scales of which being 10 −12 and 10 −14 s, respectively. This discovery provides more possibilities for the design of molecular devices with higher performance.

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Section: Introductionmentioning

confidence: 99%

Regulable Spin-Crossover Behaviors of a Family of Cyanido-Bridged Binuclear Iron(II) Compounds with a Thermally Induced Ultrafast High–Low Spin State Interconversion

Huang,

He,

Yang

et al. 2024

Crystal Growth & Design

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Chain‐Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long‐Range Electronic Interactions of Cyanido‐Bridged M₂Ru₃ (M=Fe, Ru)

Liu,

Li,

Wang

et al. 2024

Chemistry A European J

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In this work, we report the design and synthesis of two chain‐like pentanuclear cyanido‐bridged complexes trans‐[Ru(bpy)2(μ‐CN)2][cis‐Ru(bpy)2(μ‐NC)M(dppe)Cp*]2[PF6]4(M = Fe, 14+; M = Ru, 24+) and the electronic communication properties of their oxidized products 1m+ (m = 6, 7, 8) and 2n+ (n = 5, 6, 7, 8). The single‐crystal X‐ray diffraction analysis of 1m+ (m = 4, 6, 7) and 24+ show that 14+ and 24+ possess a Z‐type array structure, 17+ is a U‐type one, and 16+ exhibits both the types. The investigations indicate that both 1 and 2 show an extraordinarily strong electronic interaction between the two side Ru across the central NC‐Ru‐CN, leading to the formation of a fully delocalized cyanidometal Ru‐Ru‐Ru bridge for both three‐electron oxidized states 17+ and 27+. Moreover, it should be noted that in 1 there exists no electronic interaction between the two terminal Fe ions. Upon substitution of Fe by Ru, however, 2 exhibits an electronic interaction between the two terminal metal ions across the trinuclear cyanidometal CN‐Ru‐NC‐Ru‐CN‐Ru‐NC bridge which is up to 20 Å.

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Mixed‐Valence Electron Transfer of Cyanide‐Bridged Multimetallic Systems

Cited by 2 publications

References 79 publications

Regulable Spin-Crossover Behaviors of a Family of Cyanido-Bridged Binuclear Iron(II) Compounds with a Thermally Induced Ultrafast High–Low Spin State Interconversion

Regulable Spin-Crossover Behaviors of a Family of Cyanido-Bridged Binuclear Iron(II) Compounds with a Thermally Induced Ultrafast High–Low Spin State Interconversion

Chain‐Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long‐Range Electronic Interactions of Cyanido‐Bridged M₂Ru₃ (M=Fe, Ru)

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Mixed‐Valence Electron Transfer of Cyanide‐Bridged Multimetallic Systems

Cited by 2 publications

References 79 publications

Regulable Spin-Crossover Behaviors of a Family of Cyanido-Bridged Binuclear Iron(II) Compounds with a Thermally Induced Ultrafast High–Low Spin State Interconversion

Regulable Spin-Crossover Behaviors of a Family of Cyanido-Bridged Binuclear Iron(II) Compounds with a Thermally Induced Ultrafast High–Low Spin State Interconversion

Chain‐Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long‐Range Electronic Interactions of Cyanido‐Bridged M2Ru3 (M=Fe, Ru)

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Chain‐Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long‐Range Electronic Interactions of Cyanido‐Bridged M₂Ru₃ (M=Fe, Ru)