Assembly of photoluminescent [CunIn] (n = 4, 6 and 8) clusters by clickable hybrid [N,S] ligandsCCDC 1038927-1038930. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c5qi00030k

• Main Authors: Bai, Shi-Qiang, Jiang, Lu, Tan, Ai Lin, Yeo, Sing Chen, Young, David James, Andy Hor, T. S
• Format: Journal Article
• Language: English
• Published: 30.10.2015
• ISSN: 2052-1553
• DOI: 10.1039/c5qi00030k

Three new 1,2,3-triazole-based NS ligands, 2-((4-((benzylthio)methyl)-1 H -1,2,3-triazol-1-yl)methyl)pyridine (L1), 2-((4-(2-(cyclopentylthio)ethyl)-1 H -1,2,3-triazol-1-yl)methyl)pyridine (L2) and 2-((4-(2-(cyclopentylthio)ethyl)-1 H -1,2,3-triazol-1-yl)methyl)quinoline (L3) and the corresponding copper( i )-iodide complexes [Cu 4 I 4 (L1) 2 ] ( 1 ), [Cu 6 I 6 (L2) 2 ] ( 2 ) and [Cu 6 I 6 (L3) 2 ] ( 3A ) have been prepared and characterized by single-crystal X-ray diffraction (XRD), powder XRD, photoluminescence spectroscopy and thermogravimetric analysis. Complexes 1 , 2 and 3A exhibit stair-step [Cu n I n ] ( n = 4 and 6) cluster structures with supporting ligands L1, L2 and L3, respectively. Ligand L1 coordinates with a bidentate/monodentate binding mode in the [Cu 4 I 4 ] cluster complex 1 using the pyridyl-triazole moiety and with a pendant -CH 2 SCH 2 Ph group. Increasing the length of the bridge from -CH 2 - in L1 to -C 2 H 4 - in L2 and L3 engages the S donor and these ligands coordinate using a bidentate/monodentate/monodentate mode supporting larger [Cu 6 I 6 ] cluster complexes 2 and 3A . A kinetic product [Cu 8 I 8 (L3) 2 (CH 3 CN) 2 ] ( 3B ) was isolated from the reaction of L3 with CuI in CH 3 CN and the single-crystal X-ray structure indicates a rare discrete stair-step [Cu 8 I 8 ] core supported by two L3 and two coordinated CH 3 CN solvates. The structure is further stabilized by intermolecular π π stacking interactions in the lattice. Isolation of 1-3 provides a good demonstration of the use of multidentate and multifunctional hybrid ligands in supporting [Cu n I n ] clusters of different sizes ( n = 4, 6, 8). Ligands L1-L3 are blue emissive molecules. The corresponding complexes display strong blue ( 1 and 2 ) or remarkable yellow ( 3A ) emissions between 500 and 700 nm in the solid state. The structures of sulfur-containing ligands and their copper-iodide complexes are described and discussed. The controlled growth of luminescent copper( i )-iodide clusters has been achieved by tuning the structure of hybrid NS ligands using click chemistry.