Designable Syntheses,Structures And Properties Of D¹⁰ Metal Coordination Compounds Containing Halogen Elements

In recent years,luminescent metal-organic materials show great application on organic light emitting diodes(OLEDs),solar cells,chemical sensors,and so on.The metal coordination complexes of d10 type electron configuration are very important as luminescent materials.Especially,the cheap,accessible,eco-friendly and highly luminescent copper(I)complexes have attracted increasing attentions.In this thesis,we have successfully synthesized a series new Cu(Ⅰ)and Zn(Ⅱ)complexes containing halogen elements.The crystal structures of the complexes have been tested and analyzed by X-ray single crystal diffraction method.The complexes have been characterized by X-ray powder diffraction,elemental analyses,infrared spectra,and UV-Vis absorption spectra.The optical property and thermostability of the compounds have been studied.Combined with the TD-DFT calculation,the emission resources have been revealed.The relationship between structure and luminescent property has been preliminarily discussed.The main research of the thesis is listed as following.1.Cu(Ⅰ)complexes containing halogen elements based on the nitrogen ligands of PBI have been designed and synthesed,the structures and properties are also been studied.Two pyridinyl-benzimidazole ligands: 2-(3-pyridinyl)benzimidazole(3-PBI),2-(4-pyridinyl)benzimidazole(4-PBI)have been successfully designed and synthesized.Six new dinuclear copper(I)complexes have been synthesized by the reaction of PBI ligands,phosphine ligands and CuI:{Cu2(μ-I)2(3-PBI)2[TPP(4-CH3)]2}(1),{ Cu2(μ-I)2(3-PBI)2[TPP(3-OCH3)]2}(2),{Cu2(μ-I)2(3-PBI)2[TPP(4-OCH3)]2·CH3CN}(3),{Cu2(μ-I)2(4-PBI)2(TPP)2·C3H6O}(4),{Cu2(μ-I)2(4-PBI)2[TPP(4-CH3)]2·TPO}(5),{Cu2(μ-I)2(4-PBI)2[TPP(3-OCH3)]2 }(6).X-ray single crystal structural analyses show that all the complexes exhibit dinuclear structural type with [Cu2(μ-I)2] as centers.Coordination compounds of 3-PBI show good luminescent property at solid state.The influence of the ligands on the structures and luminescent properties of Cu(Ⅰ)complexes have been preliminarily studied.The results show that different steric phosphine ligands display different effect on the distortion of the Cu(Ⅰ)tetrahedral geometry.The stronger the electron-donating ability of the groups in the phosphine ligands shows,the shorter of emission wavelength appears.2.Cu(Ⅰ)complexes containing halogen elements based on the nitrogen ligands of pyridine have been designed and synthesed,the structures and properties are also been studied.Five copper(I)complexes have been successfully synthesized by the reaction of pyridinyl-ligand,phosphine ligand and CuI: {Cu2(μ-I)2 [Py(4-CH=CH)]2(TPP)2}(7),{Cu2(μ-I)2(Py)2[TPP(3-CH3)]2}(8),{Cu2(μ-I)2[Py(4-CH=CH)]2[TPP(3-OCH3)]2}(9),{Cu2(μ-I)2[Py(4-CH3)]2 [TPP(4-CH3)]2}(10),{Cu8(μ4–I6)(TPP)4(CN)2(H2O)}(11).X-ray single crystal structural analyses have shown that all the complexes are dinuclear copper(I)complexes with [Cu2(μ-I)2] as centers.Complex 11 exhibits a three-dimensional coordination polymeric structure with [Cu8I6(TPP)4] clusters as the nodes and CN-anions as the bridges.The complexes show good luminescent property.The relationship between structures and luminescent properties of Cu(Ⅰ)complexes have been studied preliminarily.The results show that the emission wavelength of complexes exhibit red shift when the electron-donating groups are introduced into nitrogen ligands.Different nitrogen ligands influence the energy of LUMO,which further influence the emission wavelength.The TD-DFT calculation results declare the origin of emission of coordination compounds attributed to metal-ligand charge transfer(MLCT)as well as halide-ligand charge transfer(XLCT).3.Zn(Ⅱ)coordination compounds containing halogen elements have been designed and synthesed,the structures and properties are also been studied.Three complexes have been successfully synthesized by the reaction of TPP,TPP(4-CH3),bis(diphenylphosphino)methane(dppm)and Zn I2 respectively: [ZnI2(PPh3)2](12),[ZnI2(pTol3)2](13),[ZnO6(dppm)3·ZnI4](14).The complexes display good thermal stability as well as luminescent property.The TD-DFT calculation results show that the emission of coordination compounds may derived from halide-ligand charge transfer(XLCT).