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

Autor: Antony Lapprand, Daniel Fortin, Michael Knorr, Abderrahim Khatyr, Shawkat M. Aly, Magali Allain, Pierre D. Harvey, Fabrice Guyon
Rok vydání: 2010
Předmět:
Zdroj: Journal of Inorganic and Organometallic Polymers and Materials. 20:534-543
ISSN: 1574-1451
1574-1443
DOI: 10.1007/s10904-010-9389-y
Popis: 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) A), 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. 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.
Databáze: OpenAIRE
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