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Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes

Kar, P., Guha, P. M., Drew, M. G.B., Ishida, T. and Ghosh, A. (2011) Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes. European Journal of Inorganic Chemistry, 2011 (13). pp. 2075-2085. ISSN 1434-1948

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To link to this item DOI: 10.1002/ejic.201001215

Abstract/Summary

Three new MnIII complexes, {[Mn-2(salen)(2)(OCn)](ClO4)}(n) (1), {[Mn-2(salen)(2)(OPh)](ClO4)}(n) (2) and {[Mn-2(salen)(2)(OBz)](ClO4)}(2) (3) (where salen = N,N'-bis(salicylidene)-1,2-diaminoethane dianion, OCn = cinnamate, OPh = phenylacetate and OBz = benzoate), have been synthesized and characterized structurally and magnetically. The crystal structures reveal that all three structures contain syn-anti carboxylatebridged dimeric [Mn-2(salen)(2)(OOCR)](+) cations (OOCR = bridging carboxylate) that are joined together by weak Mn center dot center dot center dot O(phenoxo) interactions to form infinite alternating chain structures in 1 and 2, but the relatively long Mn center dot center dot center dot O(phenoxo) distance [3.621(2)angstrom] in 3 restricts this structure to tetranuclear units. Magnetic studies showed that 1 and 2 exhibited magnetic long-range order at T-N = 4.0 and 4.6 K (T-N = Neel transition temperature), respectively, to give spin-canted antiferromagnetic structures. Antiferromagnetic coupling was also observed in 3 but no peaks were recorded in the field-cooled magnetization (FCM) or zero-field-cooled magnetization (ZFCM) data, indicating that 3 remained paramagnetic down to 2 K. This dominant antiferromagnetic coupling is attributed to the carboxylate bridges. The ferromagnetic coupling expected due to the Mn-O(phenoxo)center dot center dot center dot Mn bridge plays an auxiliary role in the magnetic chain, but is an essential component of the bulk magnetic properties of the material.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:30439
Publisher:Wiley-Blackwell

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