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Experimental and theoretical electron density analysis of copper pyrazine nitrate quasi-low-dimensional quantum magnets.

Dos Santos, L. H. R. and Lanza, A and Barton, A.M. and Brambleby, J. and Goddard, P. A. and Xiao, F. and Williams, R. C. and Lancaster, T. and Pratt, F. L. and Blundell, S. J. and Singleton, J. and Manson, J. L. and Macchi, P. (2016) 'Experimental and theoretical electron density analysis of copper pyrazine nitrate quasi-low-dimensional quantum magnets.', Journal of the American Chemical Society., 138 (7). pp. 2280-2291.

Abstract

The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and Density Functional Theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on Quantum Theory of Atoms in Molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed anti-ferromagnetic coupling can be quantitatively explained by the Cu-Cu super-exchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:http://dx.doi.org/10.1021/jacs.5b12817
Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jacs.5b12817.
Date accepted:26 January 2016
Date deposited:02 February 2016
Date of first online publication:26 January 2016
Date first made open access:26 January 2017

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