【作者】 李晓微；

【导师】 金为群； 程延祥；

【作者基本信息】 吉林大学 ， 应用化学， 2007， 硕士

【摘要】 本论文以β-二亚胺和三亚吡嗪类化合物为第一配体,以三苯基膦及其衍生物为第二配体设计合成了两类Cu(I)配合物,通过X光单晶衍射对其结构进行了确定和分析,同时对它们的光谱性质也进行了研究。主要结果如下:1.以β-二亚胺和三苯基膦为配体设计合成了两个单核中性Cu(I)配合物。晶体结构分析表明:两个配合物的中心铜原子分别是三配位近似平面的配位构型和四配位扭曲的四面体配位构型。两个配合物在四氢呋喃溶液中的最大吸收波长分别为376nm和411nm,在四氢呋喃溶液中的最大发射波长分别为522nm和528nm,而在20wt%浓度的PMMA薄膜中的最大发射波长为543nm和549nm。两个配合物的发光寿命分别是5.28 ns和5.32 ns。2.以三亚吡嗪类化合物和三苯基膦及其衍生物为配体合成了四种离子型的三核Cu(I)配合物。通过X-Ray单晶衍射确定了其中两种配合物的晶体结构。并测定了其中两种配合物在二氯甲烷溶液中的紫外-可见吸收光谱,其最大吸收波长分别为630nm、584nm。更多还原

【Abstract】 Luminescent materials impenetrate among the whole human history from beginning to end, especially nowadays the photon will replace electron and become information carrier increasingly. The study of photon、photochemistry and photon materials are currently receiving much attention as a technical support for information science. The diversified luminescent materials for information display are developing rapidly with the social progress and development of science and technology. The traditional inorganic luminescent materials can not meet the demand for development of science and technology. Recently the development of organic luminescent materials have obtained prodigious achievement, especially the organic metal complexes which are considered as a kind of potential luminescent materials due mainly to they have not only the property of high fluorescence efficiency but also preferable stability. The complexes consist of center ion and ligand. Many ligands can not radiate in the free form or radiate infirmly, when complexes exhibit strong luminescence because of ligands becoming much more rigid, meanwhile no-radiation transition odds decrease greatly and radiation transition odds improve remarkably.The low-cost copper（I） complexes have been applied in organic light - emitting diodes （OLEDs）, which exhibit similar emissive ability compared with heavy metal complexes e.g. iridium, ruthenium and platinum. The copper（I） complexes which composed of [Cu（phen）2]+system reported by the literatures indicate the copper（I） complexes have abundant photophysics properties. The outer layer electron of copper（I） is d¹⁰ and d-orbit is full of electrons which have none but a sort of array manner. Copper（I） complexes should be a four-coord tetrahedral geometry in theory, but in fact they have also three-coord、five-coord and even six-coord space structures. Molecule orbit reveals that the following electron transition categories emerge possibly in the copper（I） complexes system: LMCT （ligand to metal charge transfer）, The transition which is that electrons transfer from ligand to metal ion occurs currently in the ligands having upper energy lone pair electrons, and the metal ion has lower energy empty orbit; MLCT（ metal to ligand charge transfer）, This sort of transition which is that electrons transfer from metal to ligand occurs currently under the circumstance where metal ion is prone to oxidate and ligand have low energy empty orbits.The character of the transition is that eyeable or ultraviolet area have obvious absorption, absorption coefficient is in the range of 103-104, the emission occurs in the long wave area; LLCT （ligand to ligand charge transfer）, The transition which is that electrons transfer from ligand to ligand occurs popularly in the case that a sort of ligand has sole electrons whereas the other ligand has lower energyπ* empty orbit; ILCT （intraligand charge transfer）, The transition which relate to some ligands having conjugate system is intraligand charge transfer; MCCT （metal centered charge transfer）, The transition is metal centered charge transfer, MC excited state make the bond between metal and ligand weak so as to occur easily substituent reaction.Moreover MC excited state take place easily non-radiation transition, which lead optic instability and low quanta efficiency.Copper（I） complexes have manifold electron transfer excited state. They would achieve red、orange、yellow、green、blue and so on multicolour emission by choosing different ligands.In this paper we design and synthesize two mononuclear neutral copper（I） complexes as well as four three-nuclear ionic copper（I） complexes with various configuration and abundant spectrum properties of copper（I） complexes.Twoβ- dialdiminato Schiff base Cu （I） complexes have been synthesized and structurally characterized by X-ray crystallography in the second chapter. Spectrum properties and heat stability are studied at the same time. Crystal structures indicate that complex 1 is mononuclear three-coordinate and 2 is mononuclear four-coordinate. In complex 1, copper（I） atom is surrounded by one P atom from triphenylphosphine and two N atoms from ligand L1 to form a trigonal geometry, whereas in complex 2, copper（I） is coordinated by bidentate L2 and two triphenylphosphine with a distorted tetrahedral geometry. The UV-vis spectrum in THF solution exhibits two absorptions with maxima at 283 （ε= 1.99×104） and 376 （ε= 1.29×104 dm3mol-1cm-1） nm for complex 1, 274 （ε= 2.61×104） and 411 （ε= 1.18×104 dm3mol-1cm-1） nm for complex 2. The maxima emission wavelength of complex 1 and 2 in THF solution and PMMA film（20%） maxium are 528 and 549nm, respectively. Complex 1 and 2 display more extensively photoluminescence in solid state than that in liquid state or PMMA film at room temperature. Complex 1 exhibitslight yellow photoluminescence and complex 2 behaves salmon pink photoluminescence in solid state.We prepared four pyrazine copper（I） complexes in which complexes （1） and （3） have been structurally characterized by X-ray crystallography in the third chapter. Because complexes （2） and （4） are small needle shape crystalloid and powder state solid respectively, they do not fit for X-ray diffraction analysis. We conclude that （2） and （4） are the same as geometry of complexes （1） and （3） via element analysis、IR spectra of （2） and （4） as well as synthesis method. We investigate the spectrum of pyrazine copper（I） （1） and （3）. The UV-vis spectra of （1） and （3） in CH2Cl2 solution display two absorptions with maxima at 407, 630nm and 439, 584nm, respectively.更多还原