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Kucheriv OI, Shylin SI, Ksenofontov V, et al. Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines. Inorg Chem. 2016;55(10):4906-14doi: 10.1021/acs.inorgchem.6b00446.
Kucheriv, O. I., Shylin, S. I., Ksenofontov, V., Dechert, S., Haukka, M., Fritsky, I. O., & Gural'skiy, I. A. (2016). Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines. Inorganic chemistry, 55(10), 4906-14. https://doi.org/10.1021/acs.inorgchem.6b00446
Kucheriv, Olesia I, et al. "Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines." Inorganic chemistry vol. 55,10 (2016): 4906-14. doi: https://doi.org/10.1021/acs.inorgchem.6b00446
Kucheriv OI, Shylin SI, Ksenofontov V, Dechert S, Haukka M, Fritsky IO, Gural'skiy IA. Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines. Inorg Chem. 2016 May 16;55(10):4906-14. doi: 10.1021/acs.inorgchem.6b00446. Epub 2016 Apr 27. PMID: 27120049.
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Inorg Chem. 2016 May 16;55(10):4906-14. doi: 10.1021/acs.inorgchem.6b00446. Epub 2016 Apr 27.

Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines.

Inorganic chemistry

Olesia I Kucheriv, Sergii I Shylin, Vadim Ksenofontov, Sebastian Dechert, Matti Haukka, Igor O Fritsky, Il'ya A Gural'skiy

Affiliations

  1. Department of Chemistry, Taras Shevchenko National University of Kyiv , Volodymyrska St. 64, 01601 Kyiv, Ukraine.
  2. Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University of Mainz , Staudingerweg 9, D-55099 Mainz, Germany.
  3. Institute of Inorganic Chemistry, Georg August University of Göttingen , Tammannstr. 4, D-37077 Göttingen, Germany.
  4. Department of Chemistry, University of Jyväskylä , PO Box 35, FI-40014 Jyväskylä, Finland.

PMID: 27120049 DOI: 10.1021/acs.inorgchem.6b00446

Abstract

Discovery of spin-crossover (SCO) behavior in the family of Fe(II)-based Hofmann clathrates has led to a "new rush" in the field of bistable molecular materials. To date this class of SCO complexes is represented by several dozens of individual compounds, and areas of their potential application steadily increase. Starting from Fe(2+), square planar tetracyanometalates M(II)(CN)4(2-) (M(II) = Ni, Pd, Pt) and 2-substituted pyrazines Xpz (X = Cl, Me, I) as coligands we obtained a series of nine new Hofmann clathrate-like coordination frameworks. X-ray diffraction reveals that in these complexes Fe(II) ion has a pseudo-octahedral coordination environment supported by four μ4-tetracyanometallates forming its equatorial coordination environment. Depending on the nature of X and M, axial positions are occupied by two 2X-pyrazines (X = Cl and M(II) = Ni (1), Pd (2), Pt (3); X = Me and M(II) = Ni (4), Pd (5)) or one 2X-pyrazine and one water molecule (X = I and M(II) = Ni (7), Pd (8), Pt (9)), or, alternatively, two distinct Fe(II) positions with either two pyrazines or two water molecules (X = Me and M(II) = Pt (6)) are observed. Temperature behavior of magnetic susceptibility indicates that all compounds bearing FeN6 units (1-6) display cooperative spin transition, while Fe(II) ions in N5O or N4O2 surrounding are high spin (HS). Structural changes in the nearest Fe(II) environment upon low-spin (LS) to HS transition, which include ca. 10% Fe-N distance increase, lead to the cell expansion. Mössbauer spectroscopy is used to characterize the spin state of all HS, LS, and intermediate phases of 1-9 (see abstract figure). Effects of a pyrazine substituent and M(II) nature on the hyperfine parameters in both spin states are established.

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