Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 22, Issue 36, Pages 12741-12751Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201601172
Keywords
antiferromagnetic coupling; iron; molecular structures; nitrosyl complexes; spin crossover
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Funding
- Spanish Ministerio de Economia y Competitividad (MINECO)
- FEDER funds [CTQ2013-46275-P, CTQ2015-64579-C3-1-P]
- FEDER funds (Unidad de Excelencia Maria de Maeztu) [MDM-2015-0538]
- Generalitat Valenciana [PROMETEO/2012/049]
- Generalitat Valenciana
- Universidad de Valencia
- Generalitat de Catalunya
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The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF6)(2) (bztpen=N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine) displays an S=1/2 <-> S=3/2 spin crossover (SCO) behavior (T-1/2=370 K, Delta H= 12.48 kJmol(-1), Delta S=33 JK(-1) mol(-1)) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0 <-> S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120-420 K affording a detailed picture of how the electronic distribution of the t(2g)-e(g) orbitals modulates the structure of the {FeNO}(7) bond, providing valuable magneto-structural and spectroscopic correlations and DFT analysis.
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