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Unexpected Formation of a Doubly Bridged Cyclo-1,2-dithian 1D Coordination Cu2I2-Containing Luminescent Polymer

  • Michael Knorr
  • Fabrice Guyon
  • Abderrahim Khatyr
  • Magali Allain
  • Shawkat M. Aly
  • Antony Lapprand
  • Daniel Fortin
  • Pierre D. Harvey
Article

Abstract

CuI reacts instantaneously with butanedithiol in MeCN solution to form a sparingly soluble and thermally stable colorless polymeric material 1 of composition [(Cu2I2){HS(CH2)4SH}] n . Raman and IR spectroscopy confirm the presence of Cu(I) bound S–H functions. Furthermore, small amounts of the yellow compound [{Cu(μ2-I)2Cu}(C4H8S2)2] n 2 co-crystallize after several days. If the reaction mixture is exposed to air, polymeric 2 is isolated as the main product. An X-ray diffraction study reveals that 1D polymer 2 is assembled by rhomboid Cu(μ2-I)2Cu clusters (d Cu···Cu 2.6843(18) Å), which are linked through the S-atoms of six-membered 1,2-dithian heterocycles, thus generating an infinite ribbon. The low-frequency region in the Raman spectra show a striking similarity suggesting that polymers 1 and 2 bear the same cluster rhomboid Cu(μ2-I)2Cu clusters. The photophysics and luminescence properties of 2 have been studied experimentally and by means of DFT/TDDFT calculations.

Graphical Abstract

CuI reacts with HS(CH2)4SH to form a polymer of composition [(Cu2I2){HS(CH2)4SH}]n which slowly oxidizes to the luminescent [{Cu(μ2-I)2Cu}(C4H8S2)2]n polymer. The latter exhibits a 1D chain assembled by rhomboid Cu(μ2-I)2Cu clusters linked through the S-atoms of six-membered 1,2-dithian heterocycles. The luminescence properties of this polymer have been studied experimentally and by means of DFT/TDDFT calculations.

Keywords

Coordination polymer Copper Thiol Dithian DFT/TDDFT computations Thermogravimetric analysis Raman 

Notes

Acknowledgements

PDH thanks NSERC (Natural Sciences and Engineering Research Council of Canada), FQRNT (Fonds Québécois pour la Recherche en Sciences de la Nature et la Technologie) and CEMOPUS (Centre sur les Matériaux Optiques et Photoniques de l’Université de Sherbrooke) for fundings. Financial support from the council of the Région of Franche-Comté for the acquisition of a fluorescence spectrometer is also gratefully acknowledged.

Supplementary material

10904_2010_9389_MOESM1_ESM.doc (4.1 mb)
Supplementary material 1 (DOC 4231 kb)

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Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Michael Knorr
    • 1
  • Fabrice Guyon
    • 1
  • Abderrahim Khatyr
    • 1
  • Magali Allain
    • 2
  • Shawkat M. Aly
    • 3
  • Antony Lapprand
    • 3
  • Daniel Fortin
    • 3
  • Pierre D. Harvey
    • 3
  1. 1.Faculté des Sciences et des Techniques, Institut UTINAM UMR CNRS 6213Université de Franche-ComtéBesançonFrance
  2. 2.Laboratoire MOLTECH ANJOU UMR CNRS 6200Université d’AngersAngersFrance
  3. 3.Département de ChimieUniversité de SherbrookeSherbrookeCanada

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