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Photo-switchable spin-crossover iron(III) compound based on intermolecular interactions

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Abstract

Iron(III) spin-crossover compounds, [Fe(qnal)2]CF3SO3·MeOH (1·MeOH) and [Fe(qnal)2]CF3SO3·acetone (1·acetone) were prepared and their spin transition properties were characterized by magnetic susceptibility measurement, Mössbauer spectroscopy and single crystal analysis. Two iron(III) compounds exhibited abrupt spin transition with thermal hysteresis loop (T 1/2↑ = 115 K and T 1/2↓ = 104 K for 1·MeOH, and T 1/2↑ = 133 K and T 1/2↓ = 130 K for 1·acetone). Single crystal analysis revealed both of the structures in high-spin (HS) and low-spin (LS) states for 1·acetone. The difference of bond length between the HS and LS states for 1·acetone was ~0.10 Å, which was corresponding to that of typical iron(III) SCO compounds. Specially, it showed strong intermolecular interactions by π–π stacking formed between the neighbor complexes leading to 2-D sheet. Both 1·MeOH and 1·acetone exhibited LIESST effect when it was illuminated at 1000 nm. We also confirmed that the introduction of strong intermolecular interactions, such as π–π stacking, can play an important role in LIESST effect.

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References

  1. Li, F., Clegg, J.K., Goux-Capes, L., Chastanet, G., D’Alessandro, D.M., Létard, J.-F., Kepert, C.J.: A mixed-spin molecular square with a hybrid [2 × 2]grid/metallocyclic architecture. Angew. Chem. Int. Ed. 50, 2820 (2011)

    Article  CAS  Google Scholar 

  2. Ni, Z., McDaniel, A.M., Shores, M.P.: Ambient temperature anion-dependent spin state switching observed in “mostly low spin” heteroleptic iron(II) diimine complexes. Chem. Sci 1, 615 (2010)

    Article  CAS  Google Scholar 

  3. Gütlich, P., Goodwin, H.A.: Spin crossover in transition metal compounds I, II, III. Top. Curr. Chem. 233–235 (2004)

  4. Gütlich, P., Hauser, A., Spiering, H.: Thermal and optical switching of iron(II) complexes. Angew. Chem. Int. Ed. Engl. 33, 2024 (1994)

    Article  Google Scholar 

  5. Kröber, J., Codjovi, E., Kahn, O., Groliere, F., Jay, C.: A spin transition system with a thermal hysteresis at room temperature. J. Am. Chem. Soc. 115, 9810 (1993)

    Article  Google Scholar 

  6. Letard, J.-F., Guionneau, P., Codjovi, E., Lavastre, O., Bravic, G., Chasseau, D., Kahn, O.: Wide thermal hysteresis for the mononuclear spin-crossover compound cis-Bis(thiocyanato)bis[N-(2′1-pyridylmethylene)-4-(phenylethynyl)aniline]iron(II). J. Am. Chem. Soc. 119, 10861 (1997)

    Article  CAS  Google Scholar 

  7. Niel, V., Martinez-Agudo, J.M., Munoz, M.C., Gaspar, A.B., Real, J.A.: Cooperative spin crossover behavior in cyanide-bridged Fe(II)-M(II) bimetallic 3D Hofmann-like networks (M = Ni, Pd, and Pt). Inorg. Chem 40, 3838 (2001)

    Article  CAS  Google Scholar 

  8. Vreugdenhil, W., Van Diemen, J.H., De Graaff, R.A.G., Haasnoot, J.G., Reedijk, J., Van der Kraan, A.M., Kahn, O., Zarembowitch, J.: High-spin α low-spin transition in [Fe(NCS)2(4,4′-bis-1,2,4-triazole)2](H2O). X-ray crystal structure and magnetic, mössbauer and EPR properties. Polyhedron 9, 2971 (1990)

    Article  CAS  Google Scholar 

  9. Real, J.A., Andres, E., Munoz, M.C., Julve, M., Granier, T., Bousseksou, A., Varret, F.: Spin crossover in a catenane supramolecular system. Science 268, 265 (1995)

    Article  CAS  Google Scholar 

  10. Real, J.A., Gaspar, A.B., Munoz, M.C.: Thermal, pressure and light switchable spin-crossover materials. Dalton Trans. 2062 (2005)

  11. Decurtins, S., Gütlich, P., Köhler, C.P., Spiering, H., Hauser, A.: Light-induced excited spin state trapping in a transition metal complex: the hexakis(1-propyltetrazole)iron(II) tetrafluoroborate spin-crossover system. Chem. Phys. Lett. 105, 1 (1984)

    Article  CAS  Google Scholar 

  12. Decurtins, S., Gütlich, P., Koehler, C.P., Spiering, H.: New example of light-induced excited spin state trapping (LIESST) in iron(II) spin-crossover systems. J. Chem. Soc., Chem. Comm. 430 (1985)

  13. Poganiuch, P., Gütlich, P.: Light-induced excited-spin-state trapping (LIESST) in iron [Fe(2-Y-phen)3]X2 spin-crossover compounds. Inorg. Chem. 26, 455 (1987)

    Article  CAS  Google Scholar 

  14. Buchen, T., Gütlich, P., Goodwin, H.A.: Non-first-order kinetics of the high spin-low spin relaxation in [Fe(bpp)2](BF4)2 after LIESST and thermal spin trapping. Inorg. Chem. 33, 4573 (1994)

    Article  CAS  Google Scholar 

  15. Hayami, S., Gu, Z.-Z., Shiro, M., Einaga, Y., Fujishima, A., Sato, O.: First observation of light-induced excited spin state trapping for iron(III) complex. J. Am. Chem. Soc. 122, 11569 (2000)

    Article  CAS  Google Scholar 

  16. Hayami, S., Gu, Z.-Z., Yoshiki, H., Fujishima, A., Sato, O.: Iron(III) spin-crossover compounds with a wide apparent thermal hysteresis around room temperature. J. Am. Chem. Soc. 123, 11644 (2001)

    Article  CAS  Google Scholar 

  17. Juhasz, G., Hayami, S., Sato, O., Maeda, Y.: Photo-induced spin transition for iron(III) compounds with π-π interactions. Chem. Phys. Lett. 364, 164 (2002)

    Article  CAS  Google Scholar 

  18. Hayami, S., Hiki, K., Kawahara, T., Maeda, Y., Urakami, D., Inoue, K., Ohama, M., Kawata, S., Sato, O.: Photo-induced spin transition of iron(III) compounds with π-π intermolecular interactions. Chem. Eur. J 15, 3497 (2009)

    Article  CAS  Google Scholar 

  19. Lawthers, I., McGarvey, J.J.: Spin-state relaxation dynamics in iron(III) complexes: photochemical perturbation of the 2T ⇄ 6A spin equilibrium by pulsed-laser irradiation in the ligand-to-metal charge-transfer absorption band. J. Am. Chem. Soc. 106, 4280 (1984)

    Article  CAS  Google Scholar 

  20. Schenker, S., Hauser, A.: Low-temperature tunneling in the spin-state relaxation dynamics of iron(III) spin-crossover compounds. J. Am. Chem. Soc. 116, 5497 (1994)

    Article  CAS  Google Scholar 

  21. Schenker, S., Hauser, A., Dyson, R.M.: Intersystem crossing dynamics in the iron(III) spin-crossover compounds [Fe(acpa)2]PF6 and [Fe(Sal2tr)]PF6. Inorg. Chem. 35, 4676 (1996)

    Article  CAS  Google Scholar 

  22. Enachescu, C., Hauser, A., Girerd, J.J., Boillot, M.L.: Photoexcitation and relaxation dynamics of catecholato-iron(III) spin-crossover complexes. ChemPhysChem 7, 1127 (2006)

    Article  CAS  Google Scholar 

  23. Hauser, A.: Intersystem crossing in the hexakis(1-propyltetrazole)iron(2+) bis(tetrafluoroborate(1−) ([Fe(ptz)6](BF4)2) spin crossover system (ptz = 1-propyltetrazole). J. Chem. Phys. 94, 2741 (1991)

    Article  CAS  Google Scholar 

  24. Hauser, A., Vef, A., Adler, P.: Intersystem crossing dynamics in iron(II) coordination compounds. J. Chem. Phys. 95, 8710 (1991)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We thank for the financial support the Grant-in-Aids for Science Research (No. 20350028) from the Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government and for Priority Area “Coordination Programming” (area 2107) from the MEXT of Japan.Y. H. L. was also supported by the JSPS program of Postdoctoral Fellowships for Foreign Researchers (No. 2200341).

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto, 860-8555, Japan

    Tetsuya Shimizu, Yasuka Komatsu, Hidenobu Kamihata, Young Hoon Lee & Shinya Hayami

  2. Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan

    Akira Fuyuhiro

  3. National Institute of Advanced Industrial Science and Technology, Tsukuba, 305-8566, Japan

    Seiichiro Iijima

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  1. Tetsuya Shimizu
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  2. Yasuka Komatsu
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Correspondence to Shinya Hayami.

Electronic supplementary material

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10847_2011_9960_MOESM1_ESM.doc

Crystallographic data (CIF) for 1·MeOH, the selected bond lengths and angles for 1·acetone (Table S1), ORTEP drawings and packing views for 1·acetone at 120 and 200 K (Figs. S1, S2) (DOC 13 kb)

10847_2011_9960_MOESM2_ESM.pdf

Crystallographic data (CIF) for 1·MeOH, the selected bond lengths and angles for 1·acetone (Table S1), ORTEP drawings and packing views for 1·acetone at 120 and 200 K (Figs. S1, S2) (PDF 654 kb)

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Shimizu, T., Komatsu, Y., Kamihata, H. et al. Photo-switchable spin-crossover iron(III) compound based on intermolecular interactions. J Incl Phenom Macrocycl Chem 71, 363–369 (2011). https://doi.org/10.1007/s10847-011-9960-3

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  • DOI: https://doi.org/10.1007/s10847-011-9960-3

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