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Issue 24, 2013

Biphenyl bridged hexadentate N6-ligands – a rigid ligand backbone for Fe(ii) spin crossover complexes

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Abstract

The novel hexadentate nitrogen based ligand N,N′-bis-(2-(1H-pyrazol-1-yl)pyridine-6-ylmethyl)-2,2′-biphenylenediamine (3) was synthesized and used for the preparation of iron Spin Crossover (SCO) complexes [Fe(3)][BF4]2 (4) and [Fe(3)][ClO4]2 (5), which differ only by the respective counter ion. These complex salts show different spin transition temperatures T1/2 (135 and 157 K, respectively). This effect was studied by the investigation of the solid state structure of different low- and high-spin isomers. All complexes of this series show closely related crystal packing regardless of the counter ion, metal (Zn/Fe) and spin state. The isomer exhibiting the lower transition temperature (4) was also investigated in respect to its photomagnetic behaviour. The LIESST process could be monitored for this complex, but no reverse-LIESST was observed. The relaxation of the photo-induced state occurs at ca. 80 K, showing a complex, three-state relaxation mechanism.

Graphical abstract: Biphenyl bridged hexadentate N6-ligands – a rigid ligand backbone for Fe(ii) spin crossover complexes

Supplementary files

Article information


Submitted
15 Oct 2012
Accepted
30 Nov 2012
First published
30 Nov 2012

Dalton Trans., 2013,42, 8575-8584
Article type
Paper

Biphenyl bridged hexadentate N6-ligands – a rigid ligand backbone for Fe(II) spin crossover complexes

S. Heider, H. Petzold, G. Chastanet, S. Schlamp, T. Rüffer, B. Weber and J. Létard, Dalton Trans., 2013, 42, 8575 DOI: 10.1039/C2DT32451B

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