Electronic structure and solution behavior of a tris(N,N'-diphenylhydrazido)manganese(IV) propeller complex

The electronic structure and magnetic properties of the manganese(IV) trihydrazide propeller complex, Li(2)Mn(κ(2)-PhN-NPh)(3)L(2) (1, L = tetrahydrofuran, diethyl ether), are explored. EPR and solid-state magnetometry studies are indicative of a high spin Mn(IV) with a S = 3/2 spin state. Solution-...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 41; no. 26; pp. 8093 - 8097
Main Authors Kondaveeti, Sandeep K, Vaddypally, Shivaiah, McCall, Jeffrey D, Zdilla, Michael J
Format Journal Article
LanguageEnglish
Published England 14.07.2012
Subjects
Diethyl ether
Electronic structure
Infrared spectroscopy
Magnetic permeability
Magnetic properties
Propellers
Solid phases
Speciation
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Summary:The electronic structure and magnetic properties of the manganese(IV) trihydrazide propeller complex, Li(2)Mn(κ(2)-PhN-NPh)(3)L(2) (1, L = tetrahydrofuran, diethyl ether), are explored. EPR and solid-state magnetometry studies are indicative of a high spin Mn(IV) with a S = 3/2 spin state. Solution-phase magnetic measurements result in a measured μ(eff) less than that expected for a S = 3/2, indicating a solution-phase equilibrium with a lower-spin species. Concentration-dependent magnetic susceptibility measurements identify clustering of 1 to an antiferromagnetically coupled multinuclear complex as the most likely explanation for the solution behavior. Comparative infrared spectroscopy in solution and solid phase are described which support speciation in solution.
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ISSN:1477-9226
1477-9234
DOI:10.1039/c2dt30493g