Journal
INORGANIC CHEMISTRY
Volume 53, Issue 17, Pages 9296-9305Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic501425x
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Funding
- DST-FIST of India
- Department of Science and Technology (DST), New Delhi, India [SR/S1/IC/0034/2012]
- UGC
- Spanish MINECO [CTQ2012-32247]
- Ramon y Cajal Fellowship [RYC-2010-05821]
- Spanish Ministerio de Economia y Competitividad [CTQ2011-23862-C02-01]
- regional Generalitat de Catalunya authority [2009SGR-1459]
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Three new trinuclear heterometallic Ni-II-Mn-II complexes have been synthesized using a [NiL] metalloligand, where H2L = N,N'-bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)(2)Mn(OCnn)(2)(CH3OH)(2)]center dot CH3OH (1), [(NiL)(2)Mn(OPh)(2)(CH3OH)(2)][(NiL)(2)Mn(OPh)(2)]center dot H2O (2), and [(NiL)(2)Mn(OSal)(2)(CH3OH)(2)]center dot 2[NiL] (3) (where OCnn = cinnamate, OPh = phenylacetate, OSal = salicylate) have been structurally characterized. In all three complexes, in addition to the double phenoxido bridge, the two terminal Ni-II atoms are linked to the central Mn-II by means of a syn-syn bridging carboxylate, giving rise to a linear structure. Complexes 1 and 2 with Ni-O-Mn angles of 97.24 and 96.43 degrees, respectively, exhibit ferromagnetic interactions (J(Ni-Mn) = +1.38 and +0.50 cm(-1), respectively), whereas 3 is antiferromagnetic (J(Ni-Mn) = 0.24 cm-1), having an Ni-O-Mn angle of 98.51 degrees. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni-O-Mn angle and J(Ni-Mn) values, which is in agreement with the experimental results.
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