Abstract
Chemical modifications of the yet reported iron(II) compound [Fe(dpp)2(NCS)2]⋅Py (dpp = dipyrido[3,2a:2’3’c]phenazine, Py = pyridine) which shows abrupt spin crossover below room temperature with large hysteresis have been made. The purpose was to stabilize different spin states at room temperature as well as to adjust the spin crossover in temperature and hysteresis width. We modified the bidentate ligand dpp by substituting hydrogens at the phenazine by different functional groups. In addition, we substituted the thiocyanate monodentate ligands by NCSe−. The spin states of these compounds have been investigated by Mössbauer spectroscopy at two temperatures and temperature depending IR spectroscopy. These methods indicating that the chemical modifications are influencing the observed spin configuration of the complexes alongside the spin crossover behavior which changed to gradual and incomplete transitions. These promising results offer interesting possibilities for chemical adjustments of the shown spin crossover systems.
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References
Gütlich, P., Hauser, A., Spiering, H.: Thermisch und Optisch Schaltbare Eisen(II)-Komplexe. Angew. Chem. 106, 2109–2141 (1994)
Gütlich, P., Goodwin, H. A.: Spin Crossover in Transition Metal Compounds I-III. Springer, Heidelberg (2004)
Renz, F.: Physical and chemical induced spin crossover. J. Phys. Conf. Ser. 217, 012022 (2010)
Unruh, D., Homenya, P., Kumar, M., Sindelar, R., Garcia, Y., Renz, F.: Spin state switching of metal complexes by visible light or hard x-rays. Dalton Trans. 45, 14008–140018 (2016)
Gütlich, P., Gaspar, A. B., Garcia, Y.: Spin state switching in iron coordination compounds. Beilstein J. Org. Chem. 9, 342–391 (2013)
Gamez, P., Sánchez Costa, J., Quesadaa, M., Aromí, G.: Iron spin-crossover compounds: From fundamental studies to practical applications. Dalton Trans. 7845–7853 (2009)
Zhong, Z. J., Tao, J. -Q., Yu, Z., Dun, C. -Y., Liu, Y. -J., You, X. -Z.: A stacking spin-crossover iron(II) compound with a large hysteresis. J. Chem. Soc., Dalton Trans. 327–328 (1998)
Kusz, J., Zubko, M., Fitch, A., Gütlich, P.: Isostructural phase transition in the spin crossover compound [Fe(dpp)2(NCS)2]py. Z. Kristallogr. 226, 576–584 (2011)
Shepherd, H. J., Palamarciuc, T., Rosa, P., Guionneau, P., Molnar, G., Letard, J. -F., Bousseksou, A.: Antagonism between extreme negative linear compression and spin crossover in [Fe(dpp)2(NCS)2]py. Angew. Chem. Int. Ed. 51, 3910–3914 (2012)
Arancibia, A., Concepción, J., Daire, N., Leiva, G., Leiva, A. M., Loeb, B., Del Rio, R., Diaz, R., Francois, A., Saldivia, M.: Electronic effects of donor and acceptor substituents on dipyrido(3,2-a:2’,3’-c)phenazine (dppz). J. Coord. Chem. 54, 323–336 (2001)
Kleineweischede, A., Mattay, J.: Synthesis of amino- and bis(bromomethyl)-substituted bi- and tetradentate n-heteroaromatic ligands: Building blocks for pyrazino-functionalized fullerene dyads. Eur. J. Org. Chem., 947–957 (2006)
Huang, H. L., Li, Z. Z., Liang, Z. H., Liu, Y. J.: Cell cycle arrest, cytotoxicity, apoptosis, DNA-binding, photocleavage, and antioxidant activity of octahedral ruthenium(II) complexes. Eur. J. Inorg. Chem., 5538–5547 (2011)
Suffren, Y., Rollet, F. -G., Levasseur-Grenon, O., Reber, C.: Ligand-centered vibrational modes as a probe of molecular and electronic structure: Raman spectroscopy of cis-Fe(1,10-phenanthroline)2(NCS)2 and trans-Fe(pyridine)4(NCS)2 at variable temperature and pressure. Polyhedron 52, 1081–1089 (2013)
Kobetic, R., Gembarovski, D., Baranovic, G., Gabelica, V.: ESI-MS studies of mixed-ligand Fe(II) complexes containing 1,10-phenanthroline and 1,10-phenanthroline-5,6-dione as ligands. J. Mass Spectrom. 43, 753–764 (2008)
Krüger, C., Augstin, P., Nemec, I., Travnicek, Z., Oshio, H., Boca, R., Renz, F.: Spin crossover in iron(III) complexes with pentadentate schiff base ligands and pseudohalido coligands. Eur. J. Inorg. Chem., 902–915 (2013)
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The authors would like to thank and acknowledge financial support from Hannover School for Nanotechnology (hsn), Leibniz Universität Hannover (LUH), Laboratory of Nano and Quantum Engineering (LNQE) and Hochschule Hannover (HsH).
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This article is part of the Topical Collection on Proceedings of the International Conference on the Applications of the Mössbauer Effect (ICAME 2017), Saint-Petersburg, Russia, 3-8 September 2017 Edited by Valentin Semenov
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Natke, D., Unruh, D., Dreyer, B. et al. Tuning spin transitions of iron(II)-dpp systems. Hyperfine Interact 239, 12 (2018). https://doi.org/10.1007/s10751-017-1486-7
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DOI: https://doi.org/10.1007/s10751-017-1486-7