Magnetostructural Relationships For Fe(III) Spin Crossover Complexes

Abstract

Structural data for fifteen complexes of Fe(III) of a general formula [FeL5X], with pentadentate Schiff-base ligands L5 and unidentate coligands X, were subjected to a statistical analysis. The multivariate methods such as Pearson correlation, cluster analysis and principal component analysis split the data into two clusters depending upon the low-spin and/or high-spin state of the complex at the temperature of the X-ray experiment. Some of these complexes exhibit a thermally induced spin crossover. The numerical analysis of the magnetic susceptibility and magnetization data for an enlarged set of Fe(III) spin crossover systems yields the enthalpy ΔH and entropy ΔS of the transition along with the transition temperature T1/2 and the solid state cooperativeness. The thermodynamic data show a mutual relationship manifesting itself by linear ΔS vs ΔH and T1/2vs ΔH correlations.

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  • BOČA, R., LINERT, W.: Is there a need for new models of the spin crossover? Monats. Chemie, 134, 2003, 199-216.

  • BOČA, R., FUKUDA, Y., GEMBICKÝ, M., HERCHEL, R., JAROŠČIAK, R., LINERT, W., RENZ, F., Yuzurihara J.: Spin crossover in mononuclear and binuclear iron(III) complexes with pentadentate Schiff−base ligands. Chem. Phys. Lett., 325, 2000, 411-419.

  • CAMBRIDGE STRUCTURAL DATABASE, Cambridge Crystallographic Data Centre, Cambridge, CB2 1EZ, United Kingdom.

  • HALCROW, M. A. (Ed.): Spin-Crossover Materials: Properties and Applications. Wiley, New York, 2013.

  • KRÜGER, C., AUGUSTÍN, P., NEMEC, I., TRÁVNÍČEK, Z., OSHIO, H., BOČA, R., RENZ, F.: Spin crossover in iron(III) complexes with pentadentate Schiff-base ligands and pseudhalido coligands. Eur. J. Inorg. Chem., 2013, 902-915.

  • KRÜGER, C., AUGUSTÍN, P., DLHÁŇ, Ľ., PAVLIK, J., MONCOĽ, J., NEMEC, I., BOČA, R., RENZ, F.: Iron(III) complexes with pentadentate Schiff-base ligands: Influence of crystal packing change and pseudohalido coligand variations on spin crossover. Polyhedron, 87, 2015, 194-201.

  • MASÁROVÁ, P., ZOUFALÝ, J., MONCOĽ, J., NEMEC, I., PAVLIK, J., GEMBICKÝ, M., TRÁVNÍČEK, Z., BOČA, R., ŠALITROŠ, I.: Spin crossover and high spin electroneutral mononuclear iron(III) Schiff base complexes involving terminal pseudohalido ligands. New. J. Chem., 39, 2015, 508-519.

  • NEMEC, I., HERCHEL, R., BOČA, R., TRÁVNÍČEK, Z., SVOBODA, I., FUESS, H., LINERT, W.: Tuning of spin crossover behaviour in iron(III) complexes involving pentadentate Schiff bases and pseudohalides. Dalton Trans., 40, 2011, 10090-10099.

  • PAVLIK, J., BOČA, R.: Established static models of the spin crossover. Eur. J. Inorg. Chem., 2013, 697-709.

  • SORAI, M.: Calorimetric investigations of phase transitions in which electrons are directly involved. J. Chem. Thermodyn., 34, 2002, 1207-1253.

  • STATGRAPHICS CENTURION XV. Statpoint Inc., 2006.

  • ŠALITROŠ, I., BOČA, R., DLHÁŇ, Ľ., GEMBICKÝ, M., KOŽÍŠEK, J., LINARES, J., MONCOĽ, J., NEMEC, I., PERAŠÍNOVÁ, L., RENZ, F., SVOBODA, I., FUESS, H.: Unconventional spin crossover in dinuclear and trinuclear iron(III) complexes with cyanido and metallacyanido bridges. Eur. J. Inorg. Chem., 2009, 3141-3154.

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