Reactivity of CuI and CuBr toward Et2S: a Reinvestigation on the Self-Assembly of Luminescent Copper(I) Coordination Polymers

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• 作者：Michael Knorr ; Abdoulaye Pam ; Abderrahim Khatyr ; Carsten Strohmann ; Marek M. Kubicki ; Yoann Rousselin ; Shawkat M. Aly ; Daniel Fortin ; Pierre D. Harvey
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：July 5, 2010
• 年：2010
• 卷：49
• 期：13
• 页码：5834-5844
• 全文大小：1034K
• 年卷期：v.49,no.13(July 5, 2010)
• ISSN：1520-510X

文摘

CuI reacts with SEtb>2b> in hexane to afford the known strongly luminescent 1D coordination polymer [(Etb>2b>S)b>3b>{Cub>4b>(μb>3b>-I)b>4b>}]b>nb> (<b>1b>). Its X-ray structure has been redetermined at 115, 235, and 275 K in order to address the behavior of the cluster-centered emission and is built upon Cub>4b>(μb>3b>-I)b>4b> cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging SEtb>2b> ligands. However, we could not reproduce the preparation of a coordination polymer with composition [(Etb>2b>S)b>3b>{Cub>4b>(μb>3b>-Br)b>4b>}]b>nb> as reported in Inorg. Chem. <b>1975b>, 14, 1667. In contrast, the autoassembly reaction of SEtb>2b> with CuBr results in the formation of a novel 1D coordination polymer of composition [(Cub>3b>Brb>3b>)(SEtb>2b>)b>3b>]b>nb> (<b>2b>). The crystal structure of <b>2b> has been solved at 115, 173, 195, and 235 K. The framework of the luminescent compound <b>2b> consists of a corrugated array with alternating Cu(μb>2b>-Br)b>2b>Cu rhomboids, which are connected through two bridging SEtb>2b> ligands to a tetranuclear open-cubane Cub>4b>Brb>4b> SBU, ligated on two external Cu atoms with one terminal SEtb>2b>. The solid-state luminescence spectra of <b>1b> and <b>2b> exhibit intense halide-to-metal charge-transfer emissions centered at 565 and 550 nm, respectively, at 298 K. A correlation was also noted between the change in the full width at half-maximum of the emission band between 298 and 77 K and the relative flexibility of the bridging ligand. The emission properties of these materials are also rationalized by means of density functional theory (DFT) and time-dependent DFT calculations performed on <b>1b>.