Ferro- to antiferromagnetic crossover angle in diphenoxido- and carboxylato-bridged trinuclear NiII2-MnII complexes: Experimental observations and theoretical rationalization

Piya Seth, Albert Figuerola*, Jesús Jover, Eliseo Ruiz, Ashutosh Ghosh

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

34 Scopus citations

Abstract

Three new trinuclear heterometallic NiII-MnII complexes have been synthesized using a [NiL] metalloligand, where H 2L = N,N′-bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)2Mn(OCnn)2(CH3OH)2] ·CH3OH (1), [(NiL)2Mn(OPh)2(CH 3OH)2][(NiL)2Mn(OPh)2]·H 2O (2), and [(NiL)2Mn(OSal)2(CH 3OH)2]·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 NiII atoms are linked to the central MnII 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°, respectively, exhibit ferromagnetic interactions (JNi-Mn = +1.38 and +0.50 cm-1, respectively), whereas 3 is antiferromagnetic (JNi-Mn = -0.24 cm-1), having an Ni-O-Mn angle of 98.51°. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni-O-Mn angle and JNi-Mn values, which is in agreement with the experimental results.

Original languageEnglish (US)
Pages (from-to)9296-9305
Number of pages10
JournalInorganic Chemistry
Volume53
Issue number17
DOIs
StatePublished - Sep 2 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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