The Synthesis,Structures And Luminescent Properties Of Copper Or Silver-Triazole Complexes

In this thesis, we synthesized ten Cu(I), Ag(I) complexes based on four triazole ligands under hydro/solvothermal conditions. The crystal structures of these complexes were determined by single crystal X-ray diffraction method. The phase purity of the bulky samples was confirmed by PXRD measurements. These complexes were characterized by C H N element analysis, IR and 1HNMR spectra.The luminescence properties were also investigated.The four ligands used in this thesis are as follows:3,5-dii-butyl-1#-1,2,4-triazole(3,5-lBu2tzH)3,5-dineopentyl-1#-1,2,4-triazole(3,5-(neopentyl)2tzH)3,5-diisopentyl-1,2,4-triazole-4-amine (4-NH2-3,5-(isopentyl)2tz)3,5-bis(2-methylbutyl)-1,2,4-triazole-4-amine(4-NH2-3,5-(2-methylbutyl)tz)The ten complexes and their molecular formulas:{Cu2(3,5-lBu2tz)Br}n (1){Cu2(3,5-lBu2tz)I}n (2){Cu2(3,5-lBu2tz)(CN)}n (3){Cu5[3,5-(neopentyl)2tz]3Cl2}n (4){Cu5[3,5-(neopentyl)2tz]4Cl}n (5){Cu5[3,5-(neopentyl)2tz]3Cl2}n (6){Cu3[3,5-(neopentyl)2tz]2(Br)}n (7){Ag3[4-NH2-3,5-(isopentyl)2tz]3(CN)2(NO3)}n (8){Ag[4-NH2-3,5-(isopentyl)2tz](NO3)}n (9){Ag4[4-NH2-3,5-(2-methylbutyl)tz]6(BF4)4}n (10)The main research results are summarized here:1. Complexes 1 and 2 are isostructural containing cubic Cu4X4 clusters. Whereas, only complex 2 exhibits luminescence emission at ambient temperature (298 K) and at low temperature (77 K). We observed the complexes show strong emissions when the Cu…Cu distances in the Cu4X4 clusters are close to or less than the sum of the van der Waals radii of Cu atoms (2.80 A).2. The emission of 2 at room temperature can be tentatively assigned to a cluster-centered excited state (CC) of the mixed {XMCT/(d-s)}. Nevertheless, at 77 K it displays two emission bands with different lifetimes. The strong low energy (LE) emission was assigned to a triplet cluster centered (3CC) ES, a combination of iodide to copper charge transfer (XMCT) and d-s transitions, while the weak high energy (HE) band was assigned to a triplet halide to ligand charge transfer (3XLCT) ES.3. Complex 3 displays a 2D structure involving the CN- coordination. These 2D layers are further weakly connected to each other by cuprophilic interactions (Cu… Cu distance is ca.3.2 A) and Cu…π interactions (distance between Cu(I) and the center of C≡N is ca.3.5 A) forming a 3D structure. The luminescence properties of complex 3 at room temperature (298 K) and at low temperature (77 K) have been studied. The emission at room temperature (298 K) was assigned to 3[MLCT] excited state, while to 3[MLCT] and 3[XLCT] states at low temperature (77 K).4. Complexes 4,5,6 were obtained in the same solvothermal reaction. Complex 4 shows a trigonal structure, which are connected via Cl…Cu to form a chiral chain, and therefore 4 crystallize in a chiral space group -- P61. Complexes 5 and 6 adopt 3D,2D structures, respectively. These three complexes emit different colored luminescence under UV lamp (256 nm), which can be used to separate the complexes.5. Complexes 8,9,10 contain Ag2tz3, Ag2tz2, Ag4z6 clusters, respectively.