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Issue 10, 2010
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C3 symmetric tris(phosphonate)-1,3,5-triazine ligand: homopolymetallic complexes and its radical anion

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Abstract

The ligand 2,4,6-tris(dimethoxyphosphonate)-1,3,5-triazine L has been synthesized and its single crystal X-ray structure determined. The occurrence of P[double bond, length as m-dash]O⋯π intermolecular interactions, suggested by the short P[double bond, length as m-dash]O⋯triazine distances of 3.16–3.35 Å, is observed. The electrochemical reduction of the ligand shows its electron acceptor character by the formation of a stable radical anion. The hyperfine structure observed in the EPR spectra, combined with a theoretical DFT study, evidences the full delocalization of the unpaired electron mainly on the triazine core, with some participation of the phosphonate groups. Theoretical calculations are in agreement with the experimental values of the hyperfine coupling constants of 11.81 G for Aiso31P and 1.85 G for Aiso14N. Homopolymetallic complexes, formulated as {L[Cu(hfac)2]3} (1), 1{L2[Co(hfac)2]3} (2) and 1{L2[Mn(hfac)2]3} (3) (hfac = hexafluoroacetylacetonate), have been synthesized and structurally characterized.

Graphical abstract: C 3 symmetric tris(phosphonate)-1,3,5-triazine ligand: homopolymetallic complexes and its radical anion

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Supplementary files

Article information


Submitted
17 Mar 2010
Accepted
19 May 2010
First published
12 Jul 2010

New J. Chem., 2010,34, 2319-2327
Article type
Paper

C 3 symmetric tris(phosphonate)-1,3,5-triazine ligand: homopolymetallic complexes and its radical anion

C. Maxim, A. Matni, M. Geoffroy, M. Andruh, N. G. R. Hearns, R. Clérac and N. Avarvari, New J. Chem., 2010, 34, 2319
DOI: 10.1039/C0NJ00204F

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