Thermal and Optical Switching of Iron(III) Complexes

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Binuclear iron (III) spin-crossover complexes, [Fe<SUB>2</SUB> (salten)<SUB>2</SUB>(az)] (BPh<SUB>4</SUB>)<SUB>2</SUB> (1) and [Fe<SUB>2</SUB>(salten)<SUB>2</SUB>(cc)](BPh<SUB>4</SUB>)<SUB>2</SUB> (2) (H<SUB>2</SUB>salten= 2, 2'-[iminobis(3, 1-propanediylnitrilomethylidyne)]bis-phenol, az=4, 4'-azobis-pyridine, and cc=4, 4'-(1, 2-ethenediyl)bis-pyridine), and mononuclear iron (III) spin-crossover complexes, [Fe(pap)<SUB>2</SUB>]ClO<SUB>4</SUB>·H<SUB>2</SUB>O (3) (Hpap = 2-(2-pyridylmethyleneamino)phenol) and [Fe(qsal)<SUB>2</SUB>]NCSe·CH<SUB>2</SUB>Cl<SUB>2</SUB> (4) (Hqsal = 2-[(8-quinolinylimino)methyl]-phenol), were synthesized and characterized by single-crystal X-ray diffraction, Mössbauer spectra, magnetic susceptibilities, and electronic spectra. The structures of 1 and 2 were determined in the low-spin states at 100 K and the high-spin states at 298 K. The complexes 1 and 2 exhibited the spincrossover behavior; gradual and rapid spin interconversion was observed by means of Mössbauer spectroscopy at 293 K. The structure of 3 in the high-spin state was determined at 293 K. The complex 3 exhibited the abrupt spin transition with thermal hysteresis (T<SUB>1/2</SUB>↑=180 K and T<SUB>1/2</SUB>↓=165 K). The time dependence of the magnetism and the frozen-in effect were observed for the complex 3. Furthermore, light-induced excited spin state trapping effect was observed for the first time for iron (III) complexes. The structure of 4 in the low-spin state was determined at 200 K. The complex 4 exhibited a wide thermal hysteresis loop of 180 K (T<SUB>1/2</SUB>↑ = 392 K and T <SUB>1/2</SUB>↓ = 212 K) in the first cycle, although the hysteresis loop observed for the first cycle is apparent ones. Following the first loop, it shows a two-step spin transition in warming mode (T<SUB>1/2</SUB> (S1) ↑ = 215 K and T<SUB>1/2</SUB> (S2) ↑ = 282 K) and a one-step spin transition in cooling mode (T<SUB>1/2</SUB> ↓ = 212 K).

収録刊行物

  • Journal of Nuclear and Radiochemical Sciences

    Journal of Nuclear and Radiochemical Sciences 3(2), A1-A9, 2002-12-01

    日本放射化学会

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各種コード

  • NII論文ID(NAID)
    10013978768
  • NII書誌ID(NCID)
    AA11948402
  • 本文言語コード
    ENG
  • 資料種別
    REV
  • ISSN
    13454749
  • データ提供元
    CJP書誌  J-STAGE 
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