Source:http://linkedlifedata.com/resource/pubmed/id/16180872
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
20
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pubmed:dateCreated |
2005-9-26
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pubmed:abstractText |
Two new iron(III) complexes, Fe(III)(LF*)3 (1) and FeIII(L(t-Bu*))3 (2), of remote substituted o-aminophenol-based ligands are reported; complexes 1 and 2 contain three O,N-coordinated o-iminobenzosemiquinonate(1-) radical anions with ferric centers in high-spin and low-spin configurations. The crystal structures of 1 and 2 were determined by X-ray diffraction at 100 and 293 K, and the electronic structures were established by various physical methods including Mössbauer (4-290 K) and variable-temperature (2-290 K) susceptibility measurements. Electrochemical measurements (cyclic and square-wave voltammetry) indicate primarily ligand-centered redox processes. Complex 1, with the more electron-withdrawing fluoro substituents, retains the high-spin character of the ferric ion throughout the temperature range studied (2-290 K) and exhibits, as expected, strong antiferromagnetic coupling operating between three radicals (SR = 1/2) and the high-spin Fe(III) center (SFe = 5/2) yielding an St = 1 as the ground state. In contrast, the occurrence of a thermally induced spin crossover process (SFe = 5/2 <--> SFe = 1/2) is observed for complex 2 FeIII(L(t-Bu*))3, in which more electron donating tert-butyl substituents in the ligand are present. A rationale for the control of the electronic state of ferric ions in 2 together with spin-coupling schemes for 1 and 2 are provided.
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pubmed:language |
eng
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pubmed:journal | |
pubmed:status |
PubMed-not-MEDLINE
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pubmed:month |
Oct
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pubmed:issn |
0020-1669
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pubmed:author | |
pubmed:issnType |
Print
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pubmed:day |
3
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pubmed:volume |
44
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
7099-108
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pubmed:year |
2005
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pubmed:articleTitle |
Tuning of spin transition in radical-containing iron(III) complexes by remote ligand substituents.
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pubmed:affiliation |
Max-Planck-Institute for Bioinorganic Chemistry, Mülheim an der Ruhr, Germany.
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pubmed:publicationType |
Journal Article
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