【作者】 董帅；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2011， 博士

【摘要】 卟啉和酞菁是非常重要的染料分子,其中的四个吡咯或异吲哚氮原子可以和金属元素络合而形成多种多样的配合物。酞菁其大环周围的苯环上的每个位置均可以被取代基所取代,而且取代基的位置和种类大大影响着酞菁的物理和化学性质。中心空穴的氮原子能与70多种元素配位形成配合物,包括主族金属元素、过渡金属元素、镧系金属元素、锕系金属元素等。根据中心余属原子半径的大小以及氧化态的不同,酞菁大环空穴可以容纳一个甚至两个金属(主要是碱金属元素)元素。当配位的中心金属离子半径较大时(例如稀土元素,锕系元素以及主族元素In,Sn,As,Sb,Bi等),倾向于形成八配位的三明治型二层或三层配合物。近年来,由于三明治型酞菁稀土化合物在材料科学领域巨大地潜在的应用,引起了人们极大的兴趣。主要包括分子电子学、化学传感器、电致变色材料、非线性光学器件、催化剂以及液晶材料等。花二酰亚胺(简称PDI)作为一种重要的具备显著的光学和化学稳定性的功能染料,在近二十年来一直受到人们的广泛关注。由于其易修饰性,大大增加了PDI化合物的种类,同时拓宽了这类化合物的应用范围。不管在电子器件领域,如有机场效应晶体管(OFET),有机发光二极管(OLED),太阳能电池等方面；还是在光学器件领域,如静电复印感受体、荧光传感器、激光器等方面；都引起了化学和物理科学工作者们的极大兴趣。同时,四硫富瓦烯(TTF)是良好的分子功能材料,其衍生物和金属配位化合物在分析化学、催化、分子电子器件方面有广泛的应用。本文通过改变酞菁苯环上的取代基,并应用各种光谱表征手段对酞菁的结构与性质进行深入系统的研究；将PDI引入混杂卟啉酞菁的三明治配合物中,研究了整个系统的光物理性质；在酞菁中引入TTF单元,尝试对其性质和应用进行研究。本文的工作主要有以下三个主要方面：1.花二酰亚胺修饰的混杂卟啉酞菁稀土金属配合物的合成、光谱表征和电化学性质三明治型混杂卟啉酞菁金属配合物[HEuⅢ{Pc(α-3-OC5H11)4}{TriBPP(NH2))](3) [Pc(α-3-OC5H11)4=1,8,15,22-四(3-戊氧基)酞菁,TriBPP(NH2)=5,10,15-三(对叔丁基苯基)-20-(对氨基苯基)卟啉]和N-正丁基-1,6,7,12-四(对叔丁基苯氧基)-3,4-花二单酐-9,10-单酰亚胺(2)在咪唑的存在下在甲苯中反应得到新颖的苝二酰亚胺与混杂卟啉酞菁稀土铕双层配合物相连的双体系(5)。用同样的方法反应得到卟啉与花二酰亚胺相连的化合物(4)。以2,3和4为模板化物,我们系统研究了苝二酰亚胺与混杂卟啉酞菁稀土铕双层配合物相连的双体系5的电子吸收光谱和电化学性质,结果表明化合物5在基态下三明治型混杂卟啉酞菁金属配合物部分和PDI部分之间没有相互作用。而在荧光测试中发现PDI的荧光大部分被三明治双层部分淬灭,表明化合物5在激发态下存在明显的分子内部相互作用。2.TTF取代酞菁的合成及表征酞菁(Pcs)和四硫富瓦烯(TTF)都是具有平面共轭型结构的分子,在光电磁多方面有广泛的应用。因此基于扩展酞菁的平面共轭结构考虑,作者设计合成了周边位置被四硫富瓦烯(TTF)取代的酞菁,并对配体及酞菁的合成步骤进行了改进,对各种产物进行了一系列的光谱表征。TTF取代的酞菁具有独特的性质,因为TTF的强给电子特性,使产物以其以中性态和阳离子态混合存在。作者还对三明治型含TTF结构单元的酞菁的合成做了多方面的尝试,对含有TTF单元的酞菁配体的四聚反应机理以及对合成三明治型TTF取代的酞菁配合物的实验方法的改进将是未来研究的重点。3.β位八正己基磺酰基取代的酞菁的红外光谱研究在2 cm-1的分辨率下,我们测定了一系列周边位置2,3,9,10,16,17,23,24β位八烷基磺酰基取代的酞菁M[Pc(SO2C6H13)8] [M=2H(1), Cu(2), Zn(3)]的红外光谱,我们还用密度泛函理论(DFT)中的B3LYP泛函计算模拟了1和3的红外振动光谱,通过理论计算和实验结果的对比,对红外光谱中的各个振动频率进行了详细的指认。同时我们还讨论了金属配位和酞菁周边八个磺酰基取代对于酞菁红外光谱的影响。更多还原

【Abstract】 Phthalocyanines and porphyrins are two important classes of pigments, Both series belong to a cyclic tetrapyrrole family in which the four isoindole or pyrrole nitrogen atoms are able to complex with a range of metal ions. Each position of the benzene rings around the macrocycle can be substituted by substituents, and the positions and types of the substituents greatly affect the physical and chemical properties of phthalocyanines. The hydrogen atoms of the central cavity can be replaced by more than 70 elements, almost every metal, and also some metalloids. According to the size and oxidation state of the metal, one or even two(in the case of alkalines) can be included into the phthalocyanine core. With large metal centers which favor octa-coordination (e.g. rare earths, actinides, group 4 transition metals, and main group elements such as In, Sn, As, Sb, and Bi), sandwich-type complexes in the form of double- and triple-deckers can be formed. applications. Recently, the sandwich-type phthalocyaninato double deckers have attracted great attention owing to their potential applications in materials science, mainly including molecular electronics, molecular optronics, molecular iono-electronics, chemical sensors, electrochromism, non—linear optics, e]ectrocata]ysis, liquid crystals, and germicides.Perylene-3,4;9,10-tetracarboxylic diimide (PDI) derivatives have attracted increasing attention in the past decade due to their potential applications in molecular electronics and photo devices. These dyes have generated great interest because of their outstanding photochemical and thermal stability, ease of synthetic modification, and desirable optical and redox characteristics. Tetrathiafuivalene(TTF) and it’s derivatives are excellent functional molecular materials, its metal coordination compounds are widely used in analycal chemistry, catalysis and molecular electronic devices.We systematically studied the structure and properties of the Pcs which were improved by substituents at peripheral positions by means of various kinds of characterization methods. We also introduced the PDI component to Sandwich-type bis(porphyrinato)(phthalocyaninato) metal complex and investigated the optical physical properties of the whole system. We tried to study the properties and applications of new phthalocyanine by introducing the TTF component to its peripheral position. Our research work had been focused on the following three parts: 1. Perylene Diimide-Appended Mixed (Phthalocyaninato)(Porphyrinato) Rare Earth Double-Decker Complex:Synthesis, Spectroscopy and Electrochemical PropertiesTreatment of sandwich-type mixed (phthalocyaninato)(porphyrinato) metal complex [HEuⅢ{Pc(α-3-OC5H11)4}{TriBPP(NH2)}] (3) [Pc(α-3-OC5H11)4 1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninate, TriBPP(NH2) 5,10,15-tris(4-tert-butylphenyl)-20-(4-aminophenyl)porphyrinate] with N-n-butyl-1,6,7,12-tetra(4-tert-butylphenoxyl)perylene-3,4-dicarboxylate anhydride-9,10-dicarboxylate imide (2) in the presence of imidazole in toluene afforded the novel perylene diimide-appended mixed (phthalocyaninato)(porphyrinato) europium(Ⅲ) double-decker complex (5). Porphyrin-PDI dyad 4 was also obtained by similar method. The electronic absorption spectroscopic and electrochemical properties of PDI-appended double-decker 5 and the model compounds 2,3, and 4 were studied, the results indicated that there was no considerable ground-state interaction between the double-decker unit and the PDI unit in 5. The fluorescence measurements revealed that the emission of PDI unit was effectively quenched by the double-decker unit, suggesting remarkable intramolecular interaction in 5 under excited state.2. Synthesis and Characterization of the TTF-substituted PhthalocyaninePhthalocyanines(Pcs) and tetrathiafulvalene(TTF) are all planar molecules which have largeπ-conjugated systems and are widely used in optical, electricity, and magnetism. The extension of the planarπ-conjugated structure is an effective way to improve the application of these compounds. So we designed a series of TTF-substituted Pcs and studied them by means of various spectroscopic methods. The TTF-substituted Pcs have particular properties, they are mixtures of the neutral and the radical cation states due to the strong electron-donating characteristic of TTF. The reaction mechanism of cyclic tetramerization of TTF annelated phthalonitriles, and the synthetic procedure of the sandwich-type TTF-substituted phthalocyaninato metal complexes will be the focus of our future work. 3. The Infrared Spectroscopic Characteristics of Peripheral Octa-Substituted Phthalocyanines with Hexylsulfonyl GroupsThe infrared spectroscopic data for a series of three 2,3,9,10,16,17,23,24-octakis(hexylsulfonyl)phthalocyanine compounds with eight strong electron-withdrawing hexylsulfonyl groups at the peripheral positions M[Pc(SO2C6H13)8] [M=2H(1), Cu(2), Zn(3)] have been collected with resolution of 2 cm-1. The infrared spectra of compounds 1 and 3 have also been calculated at the density functional B3LYP level. Detailed assignments of the vibrational bands in the IR spectra have been achieved through comparison of the experimental and calculated results. The influence of the metalation and the substitution of eight strong electron-withdrawing alkylsulfonyl groups on the IR characteristics of the phthalocyanines has been discussed based on the comparison between corresponding data.更多还原