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Issue 28, 2013
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Spin-crossover in a trans-[FeL2(NCS)2] family (L = triaryltriazole): remote substituent effects on spin transition modes and temperature

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Abstract

We report the syntheses, characterisations, and spin-crossover behaviours of four mononuclear trans-[Fe(L1–L4)2(NCS)2] complexes (L = 4-(p-R1-phenyl)-3,5-bis(2-pyridyl)-4H-1,2,4-triazole and 4-(p-methylphenyl)-3-(p-R2-phenyl)-5-(2-pyridyl)-4H-1,2,4-triazole, (1) R1 = Cl (L1); (2) R1 = Me (L2); (3) R2 = MeO (L3); (4) R2 = F (L4)). The X-ray single crystal structural analysis reveals that 1 and 2 crystallize in the triclinic space group P[1 with combining macron], whereas 3·0.5H2O and 4 crystallize in the monoclinic space group P21/c, and all complexes possess a similar distorted [FeN6] octahedron with two trans-positions NCS anions. Changing of the distal substituent on the phenyl ring of the triaryltriazoles causes differences in the crystal packing of the complexes that are key to their magnetic properties. Magnetic measurements indicate that 1 shows an abrupt transition with T1/2 = 235 K, 2 displays a 3 K hysteresis loop with T1/2 = 217 K and T1/2 = 220 K, 3 exhibits a gradual spin transition with T1/2 = 156 K and 4 undergoes an incomplete (70%) spin transition with T1/2 = 97 K. The substituted group effects and intermolecular interactions appear to be critical to spin transition modes and temperature in this family.

Graphical abstract: Spin-crossover in a trans-[FeL2(NCS)2] family (L = triaryltriazole): remote substituent effects on spin transition modes and temperature

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Article information


Submitted
27 Mar 2013
Accepted
29 Apr 2013
First published
01 May 2013

Dalton Trans., 2013,42, 10144-10152
Article type
Paper

Spin-crossover in a trans-[FeL2(NCS)2] family (L = triaryltriazole): remote substituent effects on spin transition modes and temperature

G. Shen, L. Qi, L. Wang, Y. Xu, J. Jiang, D. Zhu, X. Liu and X. You, Dalton Trans., 2013, 42, 10144
DOI: 10.1039/C3DT50821H

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