Metal-to-Ligand Ratio Effect on the Size of Copper Iodide and Copper Bromide Clusters in 1,4-Bis(cyclohexylthio)butane-Spanned Coordination Polymers

• Published in: Journal of cluster science 2014, Vol.25 (1), p.261-275
• Main Authors: Bonnot, Antoine, Strohmann, Carsten, Knorr, Michael, Harvey, Pierre D.
• Format: Article
• Language: English
• Subjects: Catalysis; Chemical Sciences; Chemistry; Chemistry and Materials Science; Clusters; Coordination polymers; Copper; Copper bromide; Crystal structure; Crystallography; Cubane; Data collection; Geometry; Inorganic Chemistry; Iodides; Ligands; Luminescence; Nanochemistry; Original Paper; Physical Chemistry; Polymers; Spectroscopy; Transmittance; X-rays
• ISSN: 1040-7278; 1572-8862
• DOI: 10.1007/s10876-013-0637-5

The CuX salts (X = Br, I) react with 1,4-bis(cyclohexylthio)butane, L2 , in a 1:1 ratio to form the corresponding isostructural and weakly luminescent 1D coordination polymers [(Cu 2 X 2 )(μ- L2 ) 2 ] n (X = Br, 4 ; X = I, 3 ) as determined by X-ray crystallography. The previously reported reaction of CuI with 1,4-bis(phenylthio)butane, L1 , in a 2:1 metal-to-ligand ratio provides a 2D polymer [(Cu 4 I 4 )(μ- L1 ) 2 ] n , 1 (Knorr et al., Dalton Trans 38:948–955, 2009 ), where the Cu 4 I 4 unit exhibits the common cubane structure and an intense luminescence centered at 555 and 565 nm respectively at 298 and 77 K. When CuI reacts with L2 in a 2:1 metal-to-ligand ratio, a new material 2 is formed but no X-ray structure was obtained. The intense and characteristic luminescence of polymer 2 is strongly indicative of the formation of the cubane Cu 4 I 4 unit. The new materials have been characterized by solid-state UV–Vis rasing-angle transmittance spectroscopy, luminescence spectroscopy and emission lifetime measurements. Graphical Abstract