| Copper?I?complexes with a d10 electronic configuration,which have attracted potential applications prospects used in organic light-emitting devices,light-emitting electrochemical cells,chemical sensors,solar energy conversion and photocatalyst,because of their intriguing photoluminescent properties,the less expensive,environmentally friendly and abundant resource of copper?I?complex.In this thesis,reaction of copper?I?salts with four N-heterocyclic ligands,2-?2'-Pyridyl?benzoxazole?2-PBO?,2-?3'-Pyridyl?benzoxazole?3-PBO?,2-?2'-Pyridyl?benzimidazole?PBM?and 2,2-?1,4-butanediyl?bis-1,3-benzoxazole?BBO?to obtained thirteen copper?I?complexes at room temperature.The single crystal structure of all complexes were determined and analyzed by X-ray single crystal diffraction.The complexes were characterized by IR,UV-Vis and elemental analysis.The solid-state photoluminescent,electrochemical,thermal stability and catalytic properties of all complexes were studied.The main research contents are listed as follows:1.The recent studies on copper?I?complexes was introduced.2.Five copper?I?complexes 1-5,namely,[Cu?2-PBO??PPh3?Br]·CH2Cl2?1?,[Cu?2-PBO??PPh3?2]?ClO4?·2CH2Cl2?2?,[Cu?2-PBO??PPh3?2]?BF4?·2CH2Cl2?3?,[Cu?2-PBO??PPh3?2]?PF6?·CH2Cl2?4?,[Cu?3-PBO??PPh3?2?ClO4?]·CH2Cl2?5?have been synthesized by reacted of 2-?2'-Pyridyl?benzoxazole and 2-?3'-Pyridyl?benzoxazole ligands with copper?I?salts.The structural analysis revealed that complexes 1-5 were all mononuclear and tetra-coordinated,the geometric structure around the central copper?I?ion can be described as distorted tetrahedral configuration??4=0.81-0.84?.The results of solid-state photoluminescence properties of complexes 1-5 research shows that,compared with the free2-?2'-Pyridyl?benzoxazole ligand,an obvious red-shift of 148-157 nm was observed for complexes 1-4,respectively,which may be attributed to metal-to-ligand charge-transfer?MLCT?.However,the fluorescence spectra of 5 shows two bands,the high-energy emission was due to the fluorescence emission from a ligand-centerd?*-?transition of2-?3'-Pyridyl?benzoxazole,while the latter red-shift of 39 nm emission bands are assigned to the MLCT excited state.Moreover,the electrochemical properties of complexes 1-5 have been investigated by cyclic voltammetry,by calculated the HOMO and LUMO energy levels,the photoluminescent properties of the complexes were further verified.3.A new flexible bridging ligand 2,2-?1,4-butanediyl?bis-1,3-benzoxazole were synthesized by using O-aminophenol and adipic acid as starting materials.Two coordination polymers{[Cu?BBO??PPh3?]?X?}??X=ClO4?6?,BF4?7??and a binuclear copper?I?complex[Cu2?BBO??PPh3?4]?2PF6?·2CH2Cl2?8?were obtained by the reaction of the ligand and copper?I?salts.The structural analysis revealed that in complexes 6-8,all copper?I?ions are tri-coordinated and the geometric structure can be described as planar trigonal configuration.Complexes 6 and 7 exhibits a one-dimensional coordination polymers by two2,2-?1,4-butanediyl?bis-1,3-benzoxazole bridging adjacent copper?I?ions and extending along the b axis,forming a single-stranded meso-helical chain structure that extend s into 2D layer frameworks through?···?interactions.However complex 8 shows a binuclear structure and the unit extends to a 2D supramolecular layer framework through C-H···F interactions.The results of solid-state photoluminescence properties of complexes 6-8 research shows that,compared with the ligand,the fluorescence spectra of complexes 6-8 all shows two bands,the low-energy emission peaks belong to ligand-to-ligand charge transfer?LLCT?,while the high-energy emission peaks blue-shift of 16-18 nm,which may be attributed to metal-to-ligand charge-transfer?MLCT?.Moreover,the electrochemical properties of complexes 1-5 have been investigated by cyclic voltammetry,by calculated the HOMO and LUMO energy levels,the photoluminescent properties of the complexes were further verified.4.Fivecopper?I?complexes9-13,namely,[Cu?PBM??PPh3?I]?9?,[Cu?PBM??PPh3?2]?ClO4??10?,[Cu?PBM??PPh3?2]?PF6??11?,[Cu4??2-I?2??3-I?2?PPh3?4]·2CH2Cl2?12?,[Cu2?PPh3?4?SCN?2]?13?,have been synthesized by reacted of 2-?2'-Pyridyl?benzimidazole or triphenylphosphine ligands with copper?I?salts.The structural analysis revealed that complexes 9-11 were all mononuclear and tetra-coordinated,the geometric structure can be described as distorted tetrahedral configuration??4=0.76-0.86?,complex 12 is Cu4I4 clusters complex,four copper?I?ions are connected by two?3-I and two?2-I to form a distorted chair-like conformation,both copper?I?ions in complex 13 are tetra-coordinated,they are connected by two?2-SCN to form a planar tetragonal configuration.The results of solid-state photoluminescence properties of complexes research shows that,compared with the free ligand,a n obvious red-shift of108-194 nm was observed for complexes 9-11,respectively,which may be attributed to metal-to-ligand charge-transfer?MLCT?.However,complexes 12 and 13 display the similar emission bands with the free PPh3 ligand and the emission can probably be assigned to ligand-to-ligand charge transfer of phosphine ligands?LLCT?.The catalytic properties of complex 12 research show that,12 manifests promising heterogeneous catalytic activities for the degradation of methylene blue?MB?,with degradation efficiency of 99%under ambient light,pH=3 and the temperature at 30°C.Moreover,the electrochemical properties of complexes 1-5 have been investigated by cyclic voltammetry,by calculated the HOMO and LUMO energy levels,the photoluminescent properties of the complexes were further verified. |
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