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

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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.

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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.

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  1. Faculté des Sciences et des Techniques, Institut UTINAM UMR CNRS 6213, Université de Franche-Comté, La Bouloie, 16 Route de Gray, 25030, Besançon, France

    Michael Knorr, Fabrice Guyon & Abderrahim Khatyr

  2. Laboratoire MOLTECH ANJOU UMR CNRS 6200, Université d’Angers, 2 Boulevard Lavoisier, 49045, Angers, France

    Magali Allain

  3. Département de Chimie, Université de Sherbrooke, 2550 Boulevard Université, Sherbrooke, PQ, J1K 2R1, Canada

    Shawkat M. Aly, Antony Lapprand, Daniel Fortin & Pierre D. Harvey

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  1. Michael Knorr
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Correspondence to Michael Knorr or Pierre D. Harvey.

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This paper is dedicated to Charles Pittman.

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Knorr, M., Guyon, F., Khatyr, A. et al. Unexpected Formation of a Doubly Bridged Cyclo-1,2-dithian 1D Coordination Cu2I2-Containing Luminescent Polymer. J Inorg Organomet Polym 20, 534–543 (2010). https://doi.org/10.1007/s10904-010-9389-y

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