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Spin Transfer and Magnetic Interaction via Phosphorus in Nitronyl Nitroxide Radical-Substituted Triphenylphosphine Derivatives

Rancurel, Corinne and Heise, Henrike and Köhler, Frank H. and Schatzschneider, Ulrich and Rentschler, Eva and Vidal-Gancedo, Jose and Veciana, Jaume and Sutter, Jean-Pascal (2004) Spin Transfer and Magnetic Interaction via Phosphorus in Nitronyl Nitroxide Radical-Substituted Triphenylphosphine Derivatives. Journal of Physical Chemistry A, 108 (27). pp. 5903-5914. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20170606-082254934

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Abstract

The magnetic behavior of polyradicals is usually understood on the basis of the spin polarization scheme displayed by the molecules. As far as conjugated hydrocarbon species are concerned, the spin distribution is rather well established and follows the sign alternation principle. Yet when a heteroatom is involved in the exchange pathway, the situation may become more delicate. This study concerns the involvement of a P-atom in the spin distribution and the intramolecular exchange interaction of nitronyl nitroxide radical-substituted triphenyl phosphine derivatives. The spin distribution of mono-, bi-, and tri-radical phosphine derivatives has been investigated by high-resolution fluid solution EPR and ^1H and ^(31)P MAS NMR spectroscopy. These techniques permitted one to establish that spin density is located at the phosphorus atom and showed that its sign depends on whether there is a P-lone pair or not. They also revealed the spin polarization scheme for the molecules. While these schemes are in line with ferromagnetic interaction between the radical units, the actual interactions are extremely weak as found by the magnetic studies. The experimental data are supported by DFT computations (UB3LYP/Lanl2DZ), which reproduce very well the effective spin distribution on these molecular systems except the sign inversion observed when going from the phosphine to its phosphine oxide counterpart. They also predict a very small high-spin/low-spin gap for these polyradicals.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/jp049730+DOIArticle
http://pubs.acs.org/doi/full/10.1021/jp049730%2BPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp049730%2BPublisherSupporting Information
Additional Information:© 2004 American Chemical Society. Received 19 January 2004. Published online 16 June 2004. Published in print 1 July 2004. This work was supported by the European Union TMR Research Network ERB-FMRX-CT-98-0181 (1998-2003) entitled “Molecular Magnetism:  From Materials toward Devices”. U.S. and E.R. gratefully acknowledge Prof. Dr. K. Wieghardt for access to the computational facilities at the Max-Planck-Institut für Bioanorganische Chemie.
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Funding AgencyGrant Number
European Union TMR Research NetworkERB-FMRX-CT-98-0181
Issue or Number:27
Record Number:CaltechAUTHORS:20170606-082254934
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170606-082254934
Official Citation:Spin Transfer and Magnetic Interaction via Phosphorus in Nitronyl Nitroxide Radical-Substituted Triphenylphosphine Derivatives Corinne Rancurel, Henrike Heise, Frank H. Köhler, Ulrich Schatzschneider, Eva Rentschler, Jose Vidal-Gancedo, Jaume Veciana, and Jean-Pascal Sutter The Journal of Physical Chemistry A 2004 108 (27), 5903-5914 DOI: 10.1021/jp049730+
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77960
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:06 Jun 2017 18:20
Last Modified:03 Oct 2019 18:03

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