Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 12, Issue 8, Pages 2235-2243Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200500941
Keywords
iron; magnetic properties; nitrogen heterocycles; organic-inorganic hybrid composites; photo-magnetism; spin crossover
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A new series of [mu-tris-{1,n-bis(tetrazol-1-yl)alkane-N4,N4'}iron(II)] bis(perchlorate) spin-crossover coordination polymers ([Fe(nditz)(3)](ClO4)(2)]; n=4-9) has been synthesised and characterised. The ditetrazole bridging ligands provide octahedral symmetry at the iron(II) centres while allowing the distance between iron(II) centres to be varied. These polymers have therefore been investigated to determine the effects of spacer length on their thermal and light-induced spin-transition behaviour. An increase in the number of carbon atoms in the spacer (n) raises the thermal spin-crossover temperature, while decreasing the stability of the light-induced metastable state generated through the light-induced excited spin state trapping (LIESST) effect by irradiating the sample at 530 nm. Remarkably, however, the parity of the spacer also has an effect, enabling the series of complexes to be divided into two sub-series depending on whether the bridging ligand possesses an even or an odd number of carbon atoms. An explanation at the molecular level using the single configurational coordinate (SCC) model is presented.
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