Scan Rate Dependent Spin Crossover Iron(II) Complex with Two Different Relaxations and Thermal Hysteresis fac-[FeII(HLn-Pr)3]Cl·PF6 (HLn-Pr = 2-Methylimidazol-4-yl-methylideneamino-n-propyl)

Takeshi Fujinami, Koshiro Nishi, Daisuke Hamada, Keishiro Murakami, Naohide Matsumoto, Seiichiro Iijima, Masaaki Kojima, Yukinari Sunatsuki

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Abstract

Solvent-free spin crossover FeII complex fac-[FeII(HLn-Pr)3]Cl·PF6 was prepared, where HLn-Pr denotes 2-methylimidazol-4-yl-methylideneamino-n-propyl. The magnetic susceptibility measurements at scan rate of 0.5 K min-1 showed two successive spin transition processes consisting of the first spin transition T1 centered at 122 K (T1↑ = 127.1 K, T1↓ = 115.8 K) and the second spin transition T2 centered at ca. 105 K (T2↑ = 115.8 K, T2↓ = 97.2 K). The magnetic susceptibility measurements at the scan rate of 2.0, 1.0, 0.5, 0.25, and 0.1 K min-1 showed two scan speed dependent spin transitions, while the Mössbauer spectra detected only the first spin transition T1. The crystal structures were determined at 160, 143, 120, 110, 95 K in the cooling mode, and 110, 120, and 130 K in the warming mode so as to follow the spin transition process of high-spin HS → HS(T1) → HS(T2) → low-spin LS → LS(T2) → LS(T1) → HS. The crystal structures at all temperatures have a triclinic space group P1Ì... with Z = 2. The complex-cation has an octahedral N6 coordination geometry with three bidentate ligands and assume a facial-isomer with Δ- and Λ-enantimorphs. Three imidazole groups of fac-[FeII(HLn-Pr)3]2+ are hydrogen-bonded to three Cl- ions. The 3:3 NH(imidazole)···Cl- hydrogen-bonds form a stepwise ladder assembly structure, which is maintained during the spin transition process. The spin transition process is related to the structural changes of the FeN6 coordination environment, the order-disorder of PF6- anion, and the conformation change of n-propyl groups. The Fe-N bond distance in the HS state is longer by 0.2 Å than that in the LS state. Disorder of PF6- anion is not observed in the LS state but in the HS state. The conformational changes of n-propyl groups are found in the spin transition processes except for HS → HS(T1) → HS(T2).

Original languageEnglish
Pages (from-to)7291-7300
Number of pages10
JournalInorganic Chemistry
Volume54
Issue number15
DOIs
Publication statusPublished - Aug 3 2015

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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