Assembly of photoluminescent [CunIn] (n = 4, 6 and 8) clusters by clickable hybrid [N, S] ligands. Issue 11 (23rd September 2015)

• Record Type: Journal Article
• Authors: Bai, Shi-Qiang; Jiang, Lu; Tan, Ai Lin; Yeo, Sing Chen; Young, David James; Andy Hor, T. S.
• Is Part Of: Inorganic chemistry frontiers. Volume 2:Issue 11(2015)
• Page Start: 1011
• Page End: 1018
• Publication Date: 2015-09-23
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5qi00030k
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : The controlled growth of luminescent copper(i )-iodide clusters has been achieved by tuning the structure of hybrid NS ligands using click chemistry. Abstract : 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 [Cu4 I4 (L1)2 ] (1 ), [Cu6 I6 (L2)2 ] (2 ) and [Cu6 I6 (L3)2 ] (3A ) have been prepared and characterized by single-crystal X-ray diffraction (XRD), powder XRD, photoluminescence spectroscopy and thermogravimetric analysis. Complexes1, 2 and3A 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 [Cu4 I4 ] cluster complex1 using the pyridyl–triazole moiety and with a pendant –CH2 SCH2 Ph group. Increasing the length of the bridge from –CH2 – in L1 to –C2 H4 – in L2 and L3 engages the S donor and these ligands coordinate using a bidentate/monodentate/monodentate mode supporting larger [Cu6 I6 ] cluster complexes2 and3A . A kinetic product [Cu8 I8 (L3)2 (CH3 CN)2 ] (3B ) was isolated from the reaction of L3 with CuI in CH3 CN and the single-crystal X-ray structure indicates a rare discrete stair-step [Cu8 I8 ] core supported by two L3 and two coordinated CH3 CN solvates. The structure is further stabilized by intermolecular π⋯π stacking interactions in the lattice. Isolation of1–3 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 and2 ) 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.