Designable Syntheses And Stimuli-responsive Chromic Luminescent Properties Of Cuprous Halide Coordination Compounds

Luminescent metal-organic coordination complexes show valuable application on organic light-emitting diodes,chemical sensors and so on.Among those,cuprous luminescent coordination complexes have attracted more and more attention due to their multiple structural styles and adjustable optical properties.In this thesis,by the use of new quinolinyl-benzoxazole,benzimidazole ligands and phosphine ligands,a series of mononuclear,dinuclear and tetranuclear cuprous halide coordination complexes have been synthesized.The molecular structures of complexes have been determined by X-ray single crystal diffraction.Meanwhile,the complexes have been characterized by X-ray powder diffraction,elemental analyses,infrared spectra,UV-Vis absorption spectra and thermogravimetric analyses.Combined with theoretical calculation,the luminescent properties as well as the structure-property relationship have been studied.Moreover,the thermo-chromic as well as vapor-chromic luminescent properties of the dinuclear complexes and time-dependent mechano-chromic luminescencet property of a tetranuclear complex have been innovatively studied and the mechanisms of chromic luminescent properties have been analyzed.The main research contents and results of the thesis are listed as follows:1.Designable syntheses and structure-property relationship study of cuprous halide coord-ination compounds.In this thesis,four new pyridinyl and quinolinyl-benzoxazole,benzimidazole nitrogen-donating ligands:5-tert-butyl-2-?4-pyridinyl?benzoxazole?4-PBO?5-tBu??,3-methyl-2-?3-pyridinyl?benzimidazole?3-PBI?3-CH₃??,2-?2-quinolinyl?benzoxazole?2-QBO?and 2-?2-quinolinyl?benzimidazole?2-QBI?have been designed and synthesized.We have synthesized a series of copper?I?halide complexes by the co-construction of nitrogen-containing ligands,phosphine ligands and copper?I?halide,namely:?1?CuI?2-QBO??TPP?,?2?CuI?2-QBI?[TPP?4-OCH₃?],?3?CuI[?TPP??P?]₂,?4?Cu₂??-I?₂[4-PBO?5-tBu?]₂[TPP?3-OCH₃?]₂,?5?Cu₂??-I?₂[3-PBI?3-CH₃?]₂[TPP?4-OCH₃?]₂,?6?Cu₂??-I?₂[Py?3-Ph?]₂[TPP?4-OCH₃?]₂,?7?Cu₂??-I?₂[Py?4-Ph?]₂[T PP?3-CH₃?]₂,?8?Cu₂??-I?₂[Py?4-Ph?]₂[TPP?4-OCH₃?]₂,?9?Cu₂??-I?₂[Py?4-CH=CH₂?]₂[TPP?4-C H₃?]₂.CH₂Cl₂,?10?Cu₂??-I?₂[Py?4-CH=CH₂?]₂[TPP?4-OCH₃?]₂,?11?Cu₂??-I?₂[TPP?2-CH₃?]₂?C H₃CN?₂,?12?Cu₂??-I?₂[TPP?2-OCH₃?]₂,?13?Cu₄??₃-I?₄[Py?3-Ph?]₃[TPP?2-CH₃?].The single crystal structural analyses have showed the structures of complexes to be mononuclear,dinuclear and tetranuclear types.The structural influencing factors of all the coordination complexes have been analyzed.The chelating nitrogen-containing ligands were easy to form mononuclear structure,while the terminal ones tended to form dinuclear structure.The steric hindrance of the phosphine ligands could affect the mode at the coordination center and distortion degree of coordination configuration.We have investigated the structure-property relationship of complexes.Nitrogen-containing ligands should change LUMO orbital energy levels as well as the energy gap of HOMO-LUMO,so as to regulate the luminescent properties of complexes.In addition,the introduction of electron-donating groups into the phosphine ligand can also regulate the emission wavelength of complexes.With the enhance of electron-donating property in the phosphine ligand,the maximum emission wavelength of complexes would lead to the red-shift.Combined with TD-DFT calculation,the emissions of the coordination compounds could be mainly attributed to metal-ligand charge transfer?MLCT?as well as halide-ligand charge transfer?XLCT?.2.Study on the stimuli-responsive chromic luminescent properties of cuprous halide coordination compounds.In this thesis,the thermo-chromic and vapor-chromic luminescent properties of dinuclear complexesCu₂??-I?₂[Py?4-CH₃?]₂[TPP?4-CH₃?]₂ and Cu₂??-I?₂[Py?4-CH=CH₂?]₂[TPP?4-OCH₃?]₂ have been innovatively investigated by changing the coordination mode of the coordination center.By heating or vapor diffusion,the nitrogen-containing ligands in complexes were lost or left,which could change the coordination mode and configuration of the coordination center,so as to adjust the luminescence wavelength of complexes and to realize the chromic luminescent phenomena.At the same time,the time-dependent mechano-chromic luminescent properties and mechanism of a tetranuclear complex Cu₄??₃-I?₄[Py?3-Ph?]₃[TPP?2-CH₃?]have been studied.The luminescence wavelengths of complexes could be adjusted by grinding to realize the chromic luminescent phenomena.With the extension of grinding time,the luminescence intensity of complex Cu₄??₃-I?₄[Py?3-Ph?]₃[TPP?2-CH₃?]increased and the maximum emission wavelength leaded to the red-shift.The chromic luminescent phenomena were found to be invertible.