Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets.
The accurate electron density distribution and magnetic properties of two metal--organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO) and the quasi-two-dimensional (2D) [Cu(pyz)(NO)]NO·HO, have been investigated by high-resolution single-crystal X-ray diffraction and density functio...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 7; pp. 2280 - 2292 |
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| Autores principales: | , , , , , , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
2/24/2016
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=113756659&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 113756659 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 2/24/2016 vid: 138 iid: 7 pid: 997 pub: American Chemical Society artinfo: ui: 113756659 10.1021/jacs.5b12817 ppf: 2280 ppct: 12 formats: tig: atl: Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets. aug: au: Dos Santos, Leonardo H. R. Lanza, Arianna Barton, Alyssa M. Brambleby, Jamie Blackmore, William J. A. Goddard, Paul A. Fan Xiao Williams, Robert C. Lancaster, Tom Pratt, Francis L. Blundell, Stephen J. Singleton, John Manson, Jamie L. Macchi, Piero affil: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland Department of Chemistry and Biochemistry, Eastern Washington University, 226 Science, Cheney, Washington 99004, United States Department of Physics, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, United Kingdom Department of Physics, Durham University, South Road, Durham DH1 3LE, United Kingdom ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxon OX11 0QX, United Kingdom Clarendon Laboratory, Department of Physics, University of Oxford, Oxford OX1 3PU, United Kingdom National High Magnetic Field Laboratory, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States su: Electron density Pyrazines Density functional theory X-ray diffraction Molecular orbitals Coordination polymers sug: subj: Electron density Pyrazines Density functional theory X-ray diffraction Molecular orbitals Coordination polymers ab: The accurate electron density distribution and magnetic properties of two metal--organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO) and the quasi-two-dimensional (2D) [Cu(pyz)(NO)]NO·HO, 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 antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a ι-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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
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