The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2]

Xin Zhang
  • Department of Physics and Astronomy, University of Nebraska-Lincoln, Theodore Jorgensen Hall, 855 North 16th Street, Lincoln, NE 68588-0299, USA
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, Sai Mu
  • Department of Physics and Astronomy, University of Nebraska-Lincoln, Theodore Jorgensen Hall, 855 North 16th Street, Lincoln, NE 68588-0299, USA
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, Yang Liu
  • Department of Physics and Astronomy, University of Nebraska-Lincoln, Theodore Jorgensen Hall, 855 North 16th Street, Lincoln, NE 68588-0299, USA
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, Jian Luo
  • Department of Chemistry, University of Nebraska–Lincoln, Hamilton Hall, Lincoln, NE 68588-0304, USA
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, Jian Zhang
  • Department of Chemistry, University of Nebraska–Lincoln, Hamilton Hall, Lincoln, NE 68588-0304, USA
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, Alpha T. N’Diaye
  • Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
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, Axel Enders
  • Universität Bayreuth, Physikalisches Institut, Naturwissenschaften I, Universitätsstraße 30, 95447 Bayreuth, Germany
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and Peter A. Dowben
  • Corresponding author
  • Department of Physics and Astronomy, University of Nebraska-Lincoln, Theodore Jorgensen Hall, 855 North 16th Street, Lincoln, NE 68588-0299, USA
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Abstract

The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.

  • 1.

    R. G. Miller, S. Narayanaswamy, J. L. Tallon, S. Brooker, New J. Chem. 38 (2014) 1932.

  • 2.

    M. G. Cowan, R. G. Miller, S. Brooker, Dalton Trans. 44 (2015) 2880.

  • 3.

    M. G. Cowan, J. Olguín, S. Narayanaswamy, J. L. Tallon, S. Brooker, J. Am. Chem. Soc. 134 (2012) 2892.

  • 4.

    R. G. Miller, S. Narayanaswamy, S. M. Clark, P. Dera, G. B. Jameson, J. L. Tallon, S. Brooker, Dalton Trans. 44 (2015) 20843.

  • 5.

    X. Zhang, S. Mu, G. Chastanet, N. Daro, T. Palamarciuc, P. Rosa, J.-F. Létard, J. Liu, G. E. Sterbinsky, D. A. Arena, C. Etrillard, B. Kundys, B. Doudin, P. A. Dowben, J. Phys. Chem. C 119 (2015) 16293.

  • 6.

    P. Nachimuthu, J. H. Underwood, C. D. Kemp, E. M. Gullikson, D. W. Lindle, D. K. Shuh, R. C. C. Perera, in: AIP Conf. Proc., AIP Publishing, (2004), P. 454.

  • 7.

    P. E. Blöchl, Phys. Rev. B 50 (1994) 17953.

  • 8.

    G. Kresse, J. Hafner, Phys. Rev. B 48 (1993) 13115.

  • 9.

    G. Kresse, J. Furthmüller, Phys. Rev. B 54 (1996) 11169.

  • 10.

    A. I. Liechtenstein, V. I. Anisimov, J. Zaanen, Phys. Rev. B 52 (1995) R5467.

  • 11.

    J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.

  • 12.

    J. Chen, A. J. Millis, C. A. Marianetti, Phys. Rev. B 91 (2015) 241111.

  • 13.

    X. Zhang, T. Palamarciuc, J.-F. Létard, P. Rosa, E. V. Lozada, F. Torres, L. G. Rosa, B. Doudin, P. A. Dowben, Chem. Commun. 50 (2014) 2255.

  • 14.

    J.-F. Létard, P. Guionneau, L. Goux-Capes, Towards Spin Crossover Applications, in: P. Gütlich, H. A. Goodwin (Eds.): Spin Crossover Transit. Met. Compd. III, Springer, Berlin Heidelberg (2004), P. 221–249.

  • 15.

    P. Gütlich, H. A. Goodwin, in: P. Gütlich, H. A. Goodwin (Eds.): Spin Crossover Transit. Met. Compd. I, Springer Berlin Heidelberg (2004), P. 1–47.

  • 16.

    O. Sato, J. Tao, Y.-Z. Zhang, Angew. Chem. Int. Ed. 46 (2007) 2152.

  • 17.

    J. A. Real, A. B. Gaspar, M. C. Muñoz, Dalton Trans. (2005) 2062.

  • 18.

    J.-J. Lee, H. Sheu, C.-R. Lee, J.-M. Chen, J.-F. Lee, C.-C. Wang, C.-H. Huang, Y. Wang, J. Am. Chem. Soc. 122 (2000) 5742.

  • 19.

    B. Warner, J. C. Oberg, T. G. Gill, F. El Hallak, C. F. Hirjibehedin, M. Serri, S. Heutz, M.-A. Arrio, P. Sainctavit, M. Mannini, G. Poneti, R. Sessoli, P. Rosa, J. Phys. Chem. Lett. 4 (2013) 1546.

  • 20.

    T. G. Gopakumar, M. Bernien, H. Naggert, F. Matino, C. F. Hermanns, A. Bannwarth, S. Mühlenberend, A. Krüger, D. Krüger, F. Nickel, W. Walter, R. Berndt, W. Kuch, F. Tuczek, Chem. – Eur. J. 19 (2013) 15702.

  • 21.

    J.-F. Létard, G. Chastanet, P. Guionneau, C. Desplanches, Optimizing the Stability of Trapped Metastable Spin States, in: L. a Halcrow (Ed.): Spin-Crossover Mater., John Wiley & Sons Ltd, New York (2013), P. 475–506.

  • 22.

    M. Marchivie, P. Guionneau, J. A. K. Howard, G. Chastanet, J.-F. Létard, A. E. Goeta, D. Chasseau, J. Am. Chem. Soc. 124 (2002) 194.

  • 23.

    L. Capes, J.-F. Létard, O. Kahn, Chem. – Eur. J. 6 (2000) 2246.

  • 24.

    N. Moliner, L. Salmon, L. Capes, M. C. Muñoz, J.-F. Létard, A. Bousseksou, J.-P. Tuchagues, J. J. McGarvey, A. C. Dennis, M. Castro, R. Burriel, J. A. Real, J. Phys. Chem. B 106 (2002) 4276.

  • 25.

    W. Zhang, R. Alonso-Mori, U. Bergmann, C. Bressler, M. Chollet, A. Galler, W. Gawelda, R. G. Hadt, R. W. Hartsock, T. Kroll, K. S. Kjær, K. Kubiček, H. T. Lemke, H. W. Liang, D. A. Meyer, M. M. Nielsen, C. Purser, J. S. Robinson, E. I. Solomon, Z. Sun, D. Sokaras, T. B. van Driel, G. Vankó, T.-C. Weng, D. Zhu, K. J. Gaffney, Nature 509 (2014) 345.

  • 26.

    C. Creutz, M. Chou, T. L. Netzel, M. Okumura, N. Sutin, J. Am. Chem. Soc. 102 (1980) 1309.

  • 27.

    N. Huse, H. Cho, K. Hong, L. Jamula, F. M. F. de Groot, T. K. Kim, J. K. McCusker, R. W. Schoenlein, J. Phys. Chem. Lett. 2 (2011) 880.

  • 28.

    H. T. Lemke, C. Bressler, L. X. Chen, D. M. Fritz, K. J. Gaffney, A. Galler, W. Gawelda, K. Haldrup, R. W. Hartsock, H. Ihee, J. Kim, K. H. Kim, J. H. Lee, M. M. Nielsen, A. B. Stickrath, W. Zhang, D. Zhu, M. Cammarata, J. Phys. Chem. A 117 (2013) 735.

  • 29.

    W. Zhang, K. S. Kjær, R. Alonso-Mori, U. Bergmann, M. Chollet, L. A. Fredin, R. G. Hadt, R. W. Hartsock, T. Harlang, T. Kroll, K. Kubiček, H. T. Lemke, H. W. Liang, Y. Liu, M. M. Nielsen, P. Persson, J. S. Robinson, E. I. Solomon, Z. Sun, D. Sokaras, T. B. van Driel, T.-C. Weng, D. Zhu, K. Wärnmark, V. Sundström, K. J. Gaffney, Chem. Sci. 8 (2016) 515.

  • 30.

    T. Tezgerevska, K. G. Alley, C. Boskovic, Coord. Chem. Rev. 268 (2014) 23.

  • 31.

    J. Tao, H. Maruyama, O. Sato, J. Am. Chem. Soc. 128 (2006) 1790.

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