A new pentanuclear cyano-bridged complex [{Fe II(tetraazamacrocycle)} 3{μ-NC-Fe III(CN) 5} 2]: Synthesis, spectroscopic and magnetic characterization

A new pentanuclear cyano-bridged complex [{Fe II(tetraazamacrocycle)} 3{μ-NC-Fe III(CN) 5} 2]: Synthesis, spectroscopic and magnetic characterization

Hexacyanoferrate(III) reacts with [Fe II(meso)(CH 3CN) 2](ClO 4) 2·2CH 3CN (meso = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in acetonitrile/water mixture producing the title complex, where three [Fe(meso)] 2+ units are connected by two [Fe(CN) 6] 3− anions. Molecular modeling (MM...

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Bibliographic Details
Published in:Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 70; no. 5; pp. 1029 - 1033
Main Authors: Ishiruji, Fabiana H.O., Evans, David J., Benedito, Flávio L., Nunes, Fábio S.
Format: Journal Article
Language:English
Published: England Elsevier B.V 01-10-2008
Subjects:
Cyanides - chemistry
Cyano-bridged complex
Iron - chemistry
Iron-tetraazamacrocycle
Magnetics
Models, Molecular
Molecular modeling
Molecular Structure
Mössbauer
Organometallic Compounds - chemistry
Spectrum Analysis
SQUID
Temperature
UV–vis
Cyano-bridged complex
UV–vis
Mössbauer
Iron-tetraazamacrocycle
SQUID
Molecular modeling
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Summary:Hexacyanoferrate(III) reacts with [Fe II(meso)(CH 3CN) 2](ClO 4) 2·2CH 3CN (meso = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in acetonitrile/water mixture producing the title complex, where three [Fe(meso)] 2+ units are connected by two [Fe(CN) 6] 3− anions. Molecular modeling (MM +) shows a fairly linear molecule and Mössbauer data are consistent with two terminal pentacoordinated low spin iron(II)-meso units linked to one hexacoordinated low spin iron(II)-meso through two hexacoordinated low spin iron(III) units. Spectroscopic characterization showed a typical mixed-valence charge transfer band and the degree of electron coupling was calculated to be H AB = 678 cm −1. Magnetic properties exhibited an antiferromagnetic exchange interaction between the iron(III) ions with a coupling constant J = −44 cm −1.
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ISSN:1386-1425
DOI:10.1016/j.saa.2007.10.025