Unexpected Formation of a Doubly Bridged Cyclo-1,2-dithian 1D Coordination Cu2I2-Containing Luminescent Polymer |
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Authors: | Michael Knorr Fabrice Guyon Abderrahim Khatyr Magali Allain Shawkat M. Aly Antony Lapprand Daniel Fortin Pierre D. Harvey |
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Affiliation: | 1.Faculté des Sciences et des Techniques, Institut UTINAM UMR CNRS 6213,Université de Franche-Comté,Besan?on,France;2.Laboratoire MOLTECH ANJOU UMR CNRS 6200,Université d’Angers,Angers,France;3.Département de Chimie,Université de Sherbrooke,Sherbrooke,Canada |
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Abstract: | 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) ?), 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. |
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