發(fā)布時間：2018-09-08 10:50

【摘要】：近年來,以MOFs材料為紐帶的大配位化學(xué),越來越受到專家和學(xué)者的青睞。由于有機(jī)金屬配合物較復(fù)雜的價鍵和空間結(jié)構(gòu),使其在生物醫(yī)藥、材料科學(xué)和信息能源等領(lǐng)域都有十分重要的應(yīng)用。目前,配位化學(xué)的研究領(lǐng)域已滲透到許多其它學(xué)科,這不僅使得配位化學(xué)成為眾多化學(xué)分支學(xué)科的通道和交叉點(diǎn),而且還深入到了材料、物理、信息和能源等領(lǐng)域,引起了相關(guān)工作者的密切關(guān)注。為了探索高效且結(jié)構(gòu)新穎的金屬配合物,本文合成了多種基于4-氨基苯乙酮類配體,再讓其與多種過渡金屬鹽作用制備金屬配合物。通過熒光光譜法對配體及配合物的熒光特性進(jìn)行了探究,并初步分析了配合物的電化學(xué)性質(zhì)。利用Gaussian 09程序,采用DFT算法,對已合成的配體及配合物進(jìn)行了量化計算,根據(jù)所得的量化計算結(jié)果與單晶衍射結(jié)果對比,不但對實(shí)驗(yàn)結(jié)果進(jìn)行了驗(yàn)證而且對化合物的性質(zhì)也進(jìn)行了預(yù)測。采用自然揮發(fā)和氣象擴(kuò)散法成功制備了6個化合物單晶,分別是HL1-Zn(II)的配合物、HL2-Zn(II)的配合物、HL3-Mn(II)的配合物、HL4-Mn(II)的配合物、HL5、HL6。并通過X-ray確定了它們的化學(xué)組成及結(jié)構(gòu),晶體學(xué)數(shù)據(jù)如下:HL1的化學(xué)組成為C17H17Cl N2O2,Mr=316.77,屬于單斜晶系,空間群為P2(1)/c,晶胞參數(shù):a=17.789(2)?,b=7.1127(7)?,c=6.2885(6)?,α=90°,β=97.513(10)°,γ=90°,Z=2,V=788.84(14)?3,R1=0.0600,w R2=0.1651。HL2的化學(xué)組成為C16H16N2O3,Mr=284.31,屬于三斜晶系,空間群為?P1,晶胞參數(shù):a=8.7904(7)?,b=12.0808(11)?,c=14.3999(11)?,α=68.001(8)°,β=81.114(6)°,γ=83.933(7)°,Z=4,V=1398.9(2)?3,R1=0.0666,w R2=0.1884。[Zn(L2)2]的化學(xué)組成為C32H30N4Zn O6,Mr=631.97,屬于單斜晶系,空間群為C2/c,晶胞參數(shù):a=20.8670?,b=5.4304(3)?,c=25.6526(15)?,α=90°,β=97.485(5)°,γ=90°,Z=4,V=2882.1(3)?3,R1=0.0495,w R2=0.1076。[Cu(L3)2]的化學(xué)組成為C40H34 Cu N4O4,Mr=698.25,屬于單斜晶系,空間群為?C2/c,晶胞參數(shù):a=27.435(2)?,b=5.8930(3)?,c=20.6752(14)?,α=90°,β=93.969(7)°,γ=90°,Z=4,V=3334.6(4)?3,R1=0.0618,w R2=0.1611。[Zn(L4)2]的化學(xué)組成為C34H34Zn N4O6,Mr=659.76,屬于三斜晶系,空間群為?P1,晶胞參數(shù):a=13.9414(15)?,b=17.6058(18)?,c=18.278(2)?,α=83.775(2)°,β=76.523(1)°,γ=68.321(1)°,Z=2,V=4053.0(3)?3,R1=0.0700,w R2=0.1727。HL5-Mn(II)的化學(xué)組成為C40H42Br4Cl4Mn4O16,Mr=659.764,屬于三斜晶系,空間群為?P1,晶胞參數(shù):a=9.3724(9)?,b=11.7876(16)?,c=12.3994(18)?,α=70.650(13)°,β=75.462(10)°,γ=81.085(10)°,Z=1,V=1247.1(3)?3,R1=0.0618,w R2=0.1201。
[Abstract]:In recent years, the large coordination chemistry, which is linked by MOFs materials, has attracted more and more attention from experts and scholars. Organometallic complexes have very important applications in biomedicine, material science and information energy due to their complex valence bond and space structure. At present, the research field of coordination chemistry has penetrated into many other disciplines, which not only makes coordination chemistry become the channel and intersection of many chemical branches, but also goes deep into the fields of materials, physics, information and energy, etc. Has aroused the concerned worker's close attention. In order to explore metal complexes with high efficiency and novel structure, a variety of 4-aminoacetophenone ligands were synthesized and then reacted with a variety of transition metal salts to prepare metal complexes. The fluorescence characteristics of ligands and their complexes were investigated by fluorescence spectroscopy, and the electrochemical properties of the complexes were preliminarily analyzed. Using Gaussian 09 program and DFT algorithm, the synthesized ligands and their complexes were quantified. The results were compared with the results of single crystal diffraction. Not only the experimental results are verified, but also the properties of the compounds are predicted. Six single crystals have been successfully prepared by natural volatilization and meteorological diffusion methods. They are the complexes of HL1-Zn (II) and HL-2-Zn (II), the complex of HL3-Mn (II) and the complex of HL4-Mn (II). 騫墮，

本文編號：2230303