Three new 1,2,3-triazole-based NS ligands,2-((4-((benzylthio)methyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine(L1),2-((4-(2-(cyclopentylthio)ethyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine(L2)and 2-((4-(2-(cyclopentylthio)et...Three new 1,2,3-triazole-based NS ligands,2-((4-((benzylthio)methyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine(L1),2-((4-(2-(cyclopentylthio)ethyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine(L2)and 2-((4-(2-(cyclopentylthio)ethyl)-1H-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 intermolecularπ⋯πstacking 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.展开更多
基金financial support(IMRE/12-1P0907,IMRE/14-1C0248&IMRE/15-1C0202)provided by the Institute of Materials Research and Engineering,A*STARthe National University of Singapore.
文摘Three new 1,2,3-triazole-based NS ligands,2-((4-((benzylthio)methyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine(L1),2-((4-(2-(cyclopentylthio)ethyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine(L2)and 2-((4-(2-(cyclopentylthio)ethyl)-1H-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 intermolecularπ⋯πstacking 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.
