Antiferro- to ferromagnetic crossover in diphenoxido bridged NiII2MnII complexes derived from N2O2 donor Schiff base ligands

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


Three new trinuclear NiII-MnII complexes have been synthesized using three different "metalloligands" [NiL1], [NiL2] and [NiL3] derived from the Schiff bases H2L1 = N,N′-bis(salicylidene)-1,3-pentanediamine, H2L2 = N,N′-bis(salicylidene)-1,3-propanediamine and H2L3 = N,N′-bis(salicylidene)-1,3,-diaminopropan-2-ol), respectively. In all three complexes, [(NiL1)2Mn(OOCPh)2(H2O)2]·CH3OH (1), [(NiL2)2Mn(OOCPh)2(CH3OH)2]·CH3OH (2) and [(NiL3)2Mn(OOCPh)2(H2O)2]·CH3OH (3), 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 benzoate, giving rise to a linear structure. Complex 1 with Ni-O-Mn angle of 97.35° exhibits antiferromagnetic interactions (JNi-Mn = -0.60 cm-1) whereas ferromagnetic exchange is observed in 2 and 3 (JNi-Mn = +2.00 and +1.10 cm-1 respectively) having Ni-O-Mn angle 97.34° (in 2), 97.27° (in 3). Theoretical calculations have been performed in order to understand the effect of structural parameters that can tune the magnetic properties of this type of complexes such as small differences in the Ni-O-Mn angle and/or slight variations in intermolecular contacts within the crystal.

Original languageEnglish (US)
Pages (from-to)57-63
Number of pages7
StatePublished - Oct 15 2016

Bibliographical note

Funding Information:
We are thankful to Prof. Michael G. B. Drew, School of Chemistry, The University of Reading, U.K., for helpful discussions on the crystallographic part. We thank DST-FIST, India funded Single Crystal Diffractometer Facility at the Department of Chemistry, University of Calcutta, Kolkata, India. The authors thank Department of Science and Technology (DST), New Delhi, India, for financial support (SR/S1/IC/0034/2012). P.S is thankful to UGC for research fellowship [UGC/52/Jr. Fellow (Enhancement) dated 17.01.2013]. A.F acknowledges financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) through CTQ2012-32247 and for a Ramón y Cajal Fellowship (RYC-2010-05821), and from the regional Generalitat de Catalunya authority (2014SGR-129). E.R. also thanks Generalitat de Catalunya for an ICREA Academia award. The authors thankfully acknowledge the computer resources, technical expertise and assistance provided by the CSUC (Consorci de Serveis Universitaris de Catalunya).

Publisher Copyright:
© 2016 Elsevier Ltd.


  • Crossover angle
  • Heterometallic complexes
  • Magnetic properties
  • Manganese
  • Nickel

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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