Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 21, 2014
Previous Article Next Article

A comparative synthetic, magnetic and theoretical study of functional M4Cl4 cubane-type Co(II) and Ni(II) complexes

Author affiliations

Abstract

We describe the synthesis, structures, and magnetochemistry of new M4Cl4 cubane-type cobalt(II) and nickel(II) complexes with the formula [M(μ3-Cl)Cl(HL·S)]4 (1: M = Co; 2: M = Ni), where HL·S represents a pyridyl-alcohol-type ligand with a thioether functional group, introduced to allow subsequent binding to Au surfaces. Dc and ac magnetic susceptibility data of 1 and 2 were modeled with a full spin Hamiltonian implemented in the computational framework CONDON 2.0. Although both coordination clusters 1 and 2 are isostructural, with each of their transition metal ions in a pseudo-octahedral coordination environment of four Cl atoms and N,O-donor atoms of one chelating HL·S ligand, the substantially different ligand field effects of Co(II) and Ni(II) results in stark differences in their magnetism. In contrast to compound 1 which exhibits a dominant antiferromagnetic intramolecular coupling (J = −0.14 cm−1), 2 is characterised by a ferromagnetic coupling (J = +10.6 cm−1) and is considered to be a single-molecule magnet (SMM), a feature of special interest for future surface deposition studies. An analysis based on density functional theory (DFT) was performed to explore possible magnetostructural correlations in these compounds. Using a two-J model Hamiltonian, it revealed that compound 1 has four positive and two (small) negative JCo⋯Co isotropic interactions leading to a SHS = 6 ground state. Taking into account the magnetic anisotropy, one would recover a MS = 0 ground state since D > 0 from computations. In 2, all the J constants are positive and, in this framework, the zero-field splitting energy characterising the axial anisotropy was estimated to be negative (D = −0.44 cm−1). The computational results are consistent with compound 2 being an SMM.

Graphical abstract: A comparative synthetic, magnetic and theoretical study of functional M4Cl4 cubane-type Co(ii) and Ni(ii) complexes

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 28 Jan 2014, accepted on 09 Mar 2014 and first published on 10 Mar 2014


Article type: Paper
DOI: 10.1039/C4DT00306C
Citation: Dalton Trans., 2014,43, 7847-7859
  •   Request permissions

    A comparative synthetic, magnetic and theoretical study of functional M4Cl4 cubane-type Co(II) and Ni(II) complexes

    A. Ghisolfi, K. Yu. Monakhov, R. Pattacini, P. Braunstein, X. López, C. de Graaf, M. Speldrich, J. van Leusen, H. Schilder and P. Kögerler, Dalton Trans., 2014, 43, 7847
    DOI: 10.1039/C4DT00306C

Search articles by author