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Issue 44, 2013

Effect of the counter-anion on the spin-transition properties of a family of Fe(ii) tetrazole complexes, [Fe(i4tz)6]X2 (X = ClO4, PF6, SbF6, BF4)

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Abstract

The monodentate ligand 1-isobutyl-1H-tetrazole (i4tz) was used to synthesize a series of iron(II) spin-crossover (SCO) complexes with the general formula [Fe(i4tz)6]X2, where X = ClO4 (1), PF6 (2), SbF6 (3), or BF4 (4). Upon cooling, magnetic susceptibility measurements of compounds 1, 2 and 3 show a reversible one-step spin crossover (SCO) behaviour between HS (S = 2) and LS (S = 0) states without hysteresis. The ClO4 compound shows a gradual spin transition at T1/2 = 208 K at a considerably higher temperature than the other compounds. The larger anions PF6 (T1/2 = 114 K) and SbF6 (T1/2 = 116 K) show more gradual transitions, and a “frozen-in effect” was observed after fast cooling. The crystal structure of [Fe(i4tz)6](SbF6)2 (3) was determined at 296, 200 and 100 K, revealing a reversible first-order phase transition between 200 and 100 K, accompanied by a triplication of the unit cell volume at 100 K. Temperature-dependent vibration and electronic spectroscopic measurements of compound 1 were compared with the magnetic susceptibility measurements.

Graphical abstract: Effect of the counter-anion on the spin-transition properties of a family of Fe(ii) tetrazole complexes, [Fe(i4tz)6]X2 (X = ClO4−, PF6−, SbF6−, BF4−)

Supplementary files

Article information


Submitted
26 Aug 2013
Accepted
31 Aug 2013
First published
03 Sep 2013

Dalton Trans., 2013,42, 15796-15804
Article type
Paper

Effect of the counter-anion on the spin-transition properties of a family of Fe(II) tetrazole complexes, [Fe(i4tz)6]X2 (X = ClO4, PF6, SbF6, BF4)

M. Tafili-Kryeziu, M. Weil, T. Muranaka, A. Bousseksou, M. Hasegawa, A. Jun and W. Linert, Dalton Trans., 2013, 42, 15796 DOI: 10.1039/C3DT52339J

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