Direct observation of low-temperature bistability in an iron(III) LIESST compound

  • Naoto Saigo
  • Yusuke Sekimoto
  • Manabu Nakaya
  • Ryo Ohtani
  • Msaaki Nakamura
  • Shinya Hayami
Original Article


Iron(III) Schiff base compound [Fe(pap)2]ClO4·H2O (1, and Hpap = (2-(2-pyridylmethyleneamino)phenol)) shows abrupt spin crossover (SCO) with a hysteresis (T1/2↓ = 165 K, T1/2↑ = 180 K) and anomalous light induced excited spin state trapping. In the complex 1, the existence of the interaction between molecules by π electrons is suggested from single crystal structure. An anomalous LS → HS conversion, aberrant increase of HS molar fraction, was observed at low-temperature (50 K) in 1 after rapid cooling, and interpreted in terms of bistability resulted from strong cooperative interactions.


Iron(III) complex Spin-crossover LIESST 



The authors acknowledge Grants-in-Aid from MEXT of Japan (No. 26288026 and 2506 [Science of Atomic Layers]).


  1. 1.
    Kahn, O., Martinez, C.J.: Spin-transition polymers: from molecular materials toward memory devices. Science 279, 44–48 (1998)CrossRefGoogle Scholar
  2. 2.
    Gütlich, P., Garcia, Y., Woike, T.: Photoswitchable coordination compounds. Coord. Chem. Rev. 219–221, 839–879 (2001)CrossRefGoogle Scholar
  3. 3.
    Hauser, A., Jeftić, J., Romstedt, H., Hinek, R., Spiering, H.: Cooperative phenomena and light-induced bistability in iron(II) spin-crossover compounds. Coord. Chem. Rev. 190–192, 471–491 (1999)CrossRefGoogle Scholar
  4. 4.
    Hauser, A.: Cooperative effects on the HS → LS relaxation in the [Fe(ptz)6](BF4)2 spin-crossover system. Chem. Phys. Lett. 192, 65–70 (1992)CrossRefGoogle Scholar
  5. 5.
    Hayami, S., Gu, Z., Shiro, M., Einaga, Y., Fujishima, A., Sato, O.: First observation of light-induced excited spin state trapping for an iron(III) complex. J. Am. Chem. Soc. 122, 7126–7172 (2000)CrossRefGoogle Scholar
  6. 6.
    Juhász, G., Hayami, S., Seto, O., Maeda, Y.: Photo-induced spin transition for iron (III) compounds with π–π interactions. Chem. Phys. Let. 364, 164 (2002)CrossRefGoogle Scholar
  7. 7.
    Hinek, R., Spiering, H., Gütlich, P., Hauser, A.: The [Fe(etz)6](BF4)2 spin-crossover system—part two: hysteresis in the LIESST regime. Chem. Eur. J. 2, 1435–1439 (1996)CrossRefGoogle Scholar
  8. 8.
    Desaix, A., Roubeau, O., Jeftić, J., Haasnoot, J.G., Boukheddaden, K., Codjovi, E., Linarès, J., Noguès, M., Varret, F.: Light-induced bistability in spin transition solids leading to thermal and optical hysteresis. Eur. Phys. J. B 6, 183–193 (1998)CrossRefGoogle Scholar
  9. 9.
    Boukheddaden, K., Shteto, I., Hôo, B., Varret, F.: Dynamical model for spin-crossover solids. II. Static and dynamic effects of light in the mean-field approach. Phys. Rev. B 62, 14806–14817 (2000)CrossRefGoogle Scholar
  10. 10.
    Enachescu, C., Linarès, J., Varret, F.: Comparison of static and light-induced thermal hystereses of a spin-crossover solid, in a mean-field approach. J. Phys. 13, 2481–2495 (2001)Google Scholar
  11. 11.
    Hayami, S., Maeda, Y.: Time-dependence of the magnetism of [Fe(pap)2]ClO4 and its solvent adducts; unexpected solid state effect in high-spin⇔low-spin state transition. Inorg. Chim. Acta 255, 181–184 (1997)CrossRefGoogle Scholar
  12. 12.
    Oshio, H., Kitazaki, K., Mishiro, J., Kato, N., Maeda, Y., Takashima, Y.: New spin-crossover iron(III) complexes with large hysteresis effects and time dependence of their magnetism. J. Chem. Soc. Dalton Trans. 6, 1341–1347 (1987)CrossRefGoogle Scholar
  13. 13.
    Ritter, G., König, E., Irler, W., Goodwin, H.A.: The high-spin(5T2). dblharw. low-spin(1A1) transition in solid bis[2-(2-pyridylamino)-4-(2-pyridyl)thiazoleiron(II) dinitrate. Its dependence on time and on the previous history of the specimen. Inorg. Chem. 17, 224–228 (1978)CrossRefGoogle Scholar
  14. 14.
    Nelson, S.M., Mcllroy, P.D.A., Stevenson, C.S., König, E., Ritter, G., Waigel, J.: Quadridentate versus quinquedentate co-ordination of some N5 and N3O2 macrocyclic ligands and an unusual thermally controlled quintet [right left harpoons] singlet spin transition in an iron(II) complex. J. Chem. Soc. Dalton Trans. 5, 991–995 (1986)CrossRefGoogle Scholar
  15. 15.
    Létard, J.-F., Guionneau, P., Rabardel, L., Howard, J.A.K., Goeta, A.E., Chasseau, D., Kahn, O.: Structural, magnetic, and photomagnetic studies of a mononuclear iron(II) derivative exhibiting an exceptionally abrupt spin transition. Light-induced thermal hysteresis phenomenon. Inorg. Chem. 37, 4432–4441 (1998)CrossRefGoogle Scholar
  16. 16.
    Haddad, M.S., Federer, W.D., Lynch, M.W., Hendrickson, D.N.: Spin-crossover ferric complexes: unusual effects of grinding and doping solids. Inorg. Chem. 20, 131–139 (1981)CrossRefGoogle Scholar
  17. 17.
    Haddad, M.S., Federer, W.D., Lynch, M.W., Hendrickson, D.N.: An explanation of unusual properties of spin-crossover ferric complexes. J. Am. Chem. Soc. 102, 1468–1470 (1980)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Naoto Saigo
    • 1
  • Yusuke Sekimoto
    • 1
  • Manabu Nakaya
    • 1
  • Ryo Ohtani
    • 1
  • Msaaki Nakamura
    • 1
  • Shinya Hayami
    • 1
    • 2
  1. 1.Department of Chemistry, Graduate School of Science and TechnologyKumamoto UniversityChuo-kuJapan
  2. 2.Institute of Pulsed Power Science (IPPS)Kumamoto UniversityChuo-kuJapan

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