【作者】 范瑞清；

【导师】 母瀛；

【作者基本信息】 吉林大学 ， 有机化学， 2004， 博士

【摘要】 近来由于含氮配体发光金属配合物在传感器技术和电致发光器件方面具有很好的性能而倍受关注，为了开发新型的发光材料，人们合成了大量的含氮配体的d10族金属配合物并研究了它们的发光性能。中心金属离子的改变、配体π共轭体系的大小、共轭大π键的共平面性及其刚性程度和分子母体上取代基的种类等都是调控金属配合物分子发光特性的重要因素，通过设计和修饰配体和中心金属，可以调控发光的频率和强度，这样为我们进一步设计和研制发光性能更好的金属配合物奠定了基础，从而研制出能在传感器技术、光化学和电致发光器件等方面具有应用前景的金属配合物。 近几年来，人们对吡啶二亚胺金属配合物的合成、结构和催化性能的研究较为广泛。而吡啶二亚胺作为一类很好的具有较大共轭体系的三齿含氮配体，应该是一类很好的发光化合物，但此类配体及其配合物的发光性能却至今未有报道，我们对此类化合物的发光性能很感兴趣。合成了两个吡啶二亚胺锌配合物，两个配合物分子式分别为Zn(L2)Cl2 (Zn2)和 Zn(L3)Cl2·CH3CN(Zn3)。两个配合物的晶体结构经单晶X射线衍射分析，均显示为五配位的扭曲三角双锥构型。两种配合物在室温的固态和二氯甲烷溶液中呈现蓝色荧光，这可以归因于以配体为中心的π*→π跃迁。配合物的锌中心起一个重要的作用是增强了配体的π*→π跃迁的荧光发射。利用四种吡啶二亚胺配体和CdCl2·2.5H2O反应，制备出四个镉的配合物。四个配合物的分子式为：Cd(L1)Cl2·1.5CH3CN (Cd1), Cd(L2)Cl2 (Cd2), Cd(L3)Cl2- <WP=118>·CH3CN (Cd3), 和Cd(L4)Cl2·CH3CN (Cd4)。四个配合物的晶体结构经单晶X射线衍射分析，均显示为五配位的扭曲三角双锥构型。配合物在室温的固态和二氯甲烷溶液中呈现荧光，在二氯甲烷溶液中最大发射波长范围为368~409 nm，这也可以归因于以配体为中心的π*→π跃迁。配合物中镉中心也起一个重要的作用是增强了配体的π*→π跃迁的荧光发射。以四种吡啶二亚胺配体和HgCl2在乙腈溶液中反应，分别制得了四个吡啶二亚胺汞配合物(2,6-(ArN=CMe)2C5H3NHgCl2·nCH3CN) (Ar = C6H5, n = 1.5, Hg1; Ar = 2,6-iPr2C6H3, n = 0, Hg2; Ar = 2,6-Me2C6H3, n = 1, Hg3; Ar = 2-MeC6H4, n = 1, Hg4 )，四个配合物的晶体结构经单晶X射线衍射分析，均显示为五配位的扭曲三角双锥构型。四种配合物在室温的固态和二氯甲烷溶液中呈现荧光，在二氯甲烷溶液中最大发射波长为：λ = 395, 400, 407, 和403 nm，这也可以归因于以配体为中心的π*→π跃迁。自从Brookhart等人发现α-二亚胺基Ni(Ⅱ)配合物对乙烯均聚、乙烯与极性单体共聚具有很好的催化性能以来, 设计合成新型二亚胺基后过渡金属烯烃聚合催化剂已成为聚烯烃领域的研究热点。1998年，Brookhart 和 Gibson等人报道了吡啶二亚胺基铁(Ⅱ)和钴(Ⅱ)配合物催化乙烯聚合的研究结果,引起了人们极大的兴趣。该类配合物在MAO、MMAO或烷基铝/硼助催化剂活化下,对乙烯聚合表现出很好的催化性能。令人不解的是至今未见有关吡啶二亚胺基镍(Ⅱ)配合物合成和催化性能的报道，从催化剂设计的角度考虑，由α-二亚胺系列催化剂发展到吡啶二亚胺系列催化剂，首选的研究目标应该是吡啶二亚胺基镍(Ⅱ)配合物，而不是铁(Ⅱ)和钴(Ⅱ)配合物。从分子结构和中心金属电子结构考虑，吡啶二亚胺基镍配合物应与铁、钴类似物具有相似的性质，因此我们对此类配合物的合成、结构和催化性质研究很感兴趣。以NiCl2·6H2O分别和四种吡啶二亚胺配体在乙腈溶液中反应，合成了四个镍的配合物。四个配合物的晶体结构经单晶X射线衍射分析，均显示为五配位<WP=119>的扭曲三角双锥构型。配合物Ni1-Ni4经MAO活化后对乙烯聚合表现出较低的催化活性。更多还原

【Abstract】 Recently, Luminescent coordination compounds with nitrogen-containing ligands have attracted much attention due to their good performance in sensor technologies and electroluminescent devices. The d10 metal complexes with nitrogen-containing ligands have been synthesized and their luminescent behavior studied. The change of center metal ion, the size of π-conjugated system of the ligand and the electronic effect of substituents on the ligand are important factors for modulating its luminescent properties. The frequency and intensity of the luminescence of the complex are modulated via the design of the ligand-modified and center metal, so that luminescent properties are improved based on metal coordination compounds.In recent years, more researches have been done on the syntheses, structures and catalytical properties of meal complexes with bis(imino)pyridyl ligands, while all kinds of bis(imino)pyridine are also good tridentate N-donating ligands with large π-conjugating system, they should be good luminescent compounds. However, no reports on the luminecent properties of these ligands and their complexes hase been found, we are very interested in the luminescent properties of these compounds.Two new Zn (II) complexes of 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyrid-ine(L2), 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine(L3) were synthesized. <WP=121>These two complexes have the formulas Zn(L2)Cl2(Zn2) and Zn(L3)Cl2·CH3CN(Zn3), respectively. Crystal structures of complexes Zn2 and Zn3 were determined by single-crystal X-ray diffraction. Crystallographic studies on Zn2 and Zn3 reveal both complexes to be five-coordinate with geometries that can be best described as distorted trigonal bipyramidal. Complexes Zn2 and Zn3 have blue luminescence at room temperature in solution and the solid state. The blue luminescence of the complexes is due to π*→ π transition centered on the ligands. The Zn (II) centers play a key role in enhancing fluorescent emission of the ligands. Four new Cd (II) complexes of 2,6-bis[(1-phenylimino)ethyl]pyridine (L1), 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine (L2), 2,6-bis[1-(2,6-dimethyl-phenylimino)ethyl]pyridine (L3), 2,6-bis[1-(2-methylphenylimino)ethyl]pyridine (L4) were synthesized. These four complexes have the formulas Cd(L1)Cl2·1.5CH3CN (Cd1), Cd(L2)Cl2 (Cd2), Cd(L3)Cl2·CH3CN (Cd3), and Cd(L4)Cl2·CH3CN (Cd4), respectively. The molecular structures of complexes Cd1–Cd4 were determined by single-crystal X-ray diffraction. Crystallographic studies on Cd1–Cd4 reveal all four complexes to be five-coordinate with geometries that can be best described as distorted trigonal bipyramidal. Four complexes are luminescent at room temperature in solution and the solid state. At 298 K in dichloromethane solution, all compounds have fluorescent emissions at ca. 368–409 nm. Fluorescent emission of these compounds originates from π*–π transitions centered on the ligands. The Cd (II) centers play a key role in enhancing fluorescent emission of the ligands. Four new five-coordinated 2,6-bis(imino)pyridyl mercury complexes, [2,6-(ArN=CMe)2C5H3NHgCl2·nCH3CN] (Ar = C6H5, n = 1.5, Hg1; Ar = 2,6-iPr2C6H3, n = 0, Hg2; Ar = 2,6-Me2C6H3, n = 1, Hg3; Ar = 2-MeC6H4, n = 1, Hg4 ), were synthesized in good yield by reactions of the corresponding bis(imino)pyridine ligands with HgCl2 in CH3CN solution. Crystal structures of complexes Hg1–Hg4 were determined by single-crystal X-ray diffraction. In all complexes, the metal center is tridentately chelated by ligand and further coordinated by two chlorine atoms, resulting in a distorted trigonal bipyramidal geometry. All complexes are luminescent in both solution and the solid state. At <WP=122>293K in CH2Cl2 solution, the fluorescent emission maxima for complexes Hg1–Hg4 are at λ = 395, 400, 407, and 403nm, respectively, which can be attributed to ligand-centered π*–π transitions. The mercury (II) centers play a key role in enhancing fluorescent emission of the ligands. Since Brookhart et al. found that nick更多还原