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Issue 34, 2012
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Magnetic properties of the seven-coordinated nanoporous framework material Co(bpy)1.5(NO3)2 (bpy = 4,4′-bipyridine)

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Abstract

The magnetic properties of the porous metal–organic complex Co(bpy)1.5(NO3)2 (bpy = 4,4′-bipyridine), investigated by SQUID magnetometry, EPR and heat capacity measurements, are reported. The tongue-and-groove structure of this complex is formed by the assembly of T-shaped building blocks, where each Co is bound to three bpy ligands. Co(II) is hepta-coordinated by three N atoms from the bpy units, and four O atoms from two nitrate groups. Experimental results showed a large crystal field effect induced anisotropy with a zero field splitting of Δ = 198 K between the ground and excited Kramers doublets, a factor of two larger than previously reported values in Co(II) hepta-coordinated complexes. EPR revealed orthorhombic crystal field anisotropy, with gyromagnetic principal values of g1* = 6.1, g2* = 4.2 and g3* = 2.2, in an S* = 1/2 effective spin on the ground state Kramers doublet. Ab initio simulations allowed us to assign the anisotropy easy axis of magnetization to the binary symmetry axis of the molecule, aligned with the Co–N apical direction of the T-block.

Graphical abstract: Magnetic properties of the seven-coordinated nanoporous framework material Co(bpy)1.5(NO3)2 (bpy = 4,4′-bipyridine)

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Publication details

The article was received on 25 May 2012, accepted on 06 Jul 2012 and first published on 06 Jul 2012


Article type: Paper
DOI: 10.1039/C2DT31135F
Citation: Dalton Trans., 2012,41, 10382-10389
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    Magnetic properties of the seven-coordinated nanoporous framework material Co(bpy)1.5(NO3)2 (bpy = 4,4′-bipyridine)

    E. Bartolomé, P. J. Alonso, A. Arauzo, J. Luzón, J. Bartolomé, C. Racles and C. Turta, Dalton Trans., 2012, 41, 10382
    DOI: 10.1039/C2DT31135F

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