Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 15, Issue 5, Pages 1252-1260Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200801852
Keywords
chelates; iron; magnetic properties; N ligands; spin crossover
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Funding
- EU through NE MAGMANET [FP6-NMP3-CT-2005 515767]
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This paper reports the synthesis of a family of mononuclear complexes [Fe(L)]X(2) (X=BF(4), PF(6), ClO(4)) with hexadentate ligands L=Hpy-DAPP ([bis[N-(2-pyridylmethyl)-3-aminopropyl](2-pyridylmethyl)amine)), Hpy-EPPA ([[N-(2-pyridylmethyl)-3-aminopropyl] [N-(2-pyridylmethyl)-2-aminoethyl] (2-pyridylmethyl)amine]) and Hpy-DEPA ((bis[N-(2-pyridylmethyl)-2-aminoethyl](2-pyridylmethyl)amine]). The systematic change of the length of amino-aliphatic chains in these ligands results in chelate rings of different size: two six-membered rings for Hpy-DAPP, one five- and one six-membered rings for Hpy-EPPA, and two five-membered rings for Hpy-DEPA. The X-ray analysis of three low-spin complexes [Fe(L)](BF(4))(2) revealed similarities in their molecular and crystal structures. The magnetic measurements have shown that all synthesized complexes display spin-crossover behavior. The spin-transition temperature increases upon the change from six-membered to five-membered chelate rings, clearly demonstrating the role of the ligand strain. This effect does not depend on the nature of the counter ion. We discuss the structural features accountable for the strain effect on the spin-transition temperature.
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