【作者】 张宪尧；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2011， 博士

【摘要】 卟啉酞菁类化合物以及三明治型稀土卟啉酞菁配合物具有独特的光学、电学、磁学性质,它们在分子电子学、分子信息存储和非线性光学上具有广泛潜在的应用价值,因此,可以作为拥有广阔的应用前景的新型的功能材料。卟啉以及酞菁化合物属于环状四吡咯化合物,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。当和稀土元素,锕系元素以及主族元素In, Sn, As, Sb, Bi等离子半径较大金属配位时,倾向于形成八配位的三明治型双层或三层配合物。因为两个或三个共轭大环配体在三明治型配合物中的距离很近,所以具有非常强的分子内π-π相互作用,使得这类配合物具有非常特殊的光电功能性质和应用前景,例如可以作为电致变色显示材料、场效应晶体管材料、气体传感材料以及光合作用反应中心“特殊对”的结构模型。光学活性的四吡咯大环衍生物和许多生物学过程相关,并且在很多工业方面具备广泛的应用潜力,从而激起了学者们极大的研究热情。近几十年来在太阳能转化、电致发光、以及能力传递和电子转移等领域得到广泛的应用。基于此,我们设计合成了一系列含卟啉、卟啉酞菁混杂三明治型配合物并对其性能进行了研究,为寻找新的太阳能电池材料奠定了理论基础和开辟了新的方向。以下是本文的主要工作：1、苯醚键相联的C60-卟啉二元化合物的合成、电化学和光谱性质研究设计合成了一系列苯醚键相连的C60-卟啉二元化合物及其金属锌配合物：H2Por-P-C60、H2Por-M-C60、H2Por-O-C60、ZnPor-P-C60、ZnPor-M-C60和ZnPor-O-C60,通过质谱、元素分析和核磁共振氢谱对它们的结构进行了表征。基态的电子吸收光谱和电化学研究表明在这些二元体系中C60和卟啉之间存在明显的相互作用。荧光光谱研究表明卟啉单元的荧光几乎被C60单元完全淬灭,并且它们之间的连接位置对荧光淬灭的效率具有显著影响。2、卟啉修饰的卟啉酞菁混杂三明治配合物中：连接位置决定的荧光淬灭过程研究设计并合成了三种新型的三明治型混杂卟啉酞菁稀土钇双层配合物。在三明治中卟啉一侧的meso-位苯环的邻、间、对位通过酯键分别连接了一个自由卟啉。对这三种化合物以及参比化合物四(4-叔丁基苯)卟啉H2TBPP (1)和[1,4,8,11,15,18,22,25-八(丁氧基)酞菁][四(4-叔丁基苯)卟啉]钇双层配合物HY[Pc(α-OC4H9)8](TBPP) (2)通过稳态光谱和瞬态光谱进行了光物理性质的研究。荧光光谱显示：卟啉和三明治在间位、对位通过酯键连接的化合物中,卟啉的荧光完全被淬灭,。而邻位连接的化合物中,卟啉的荧光是部分淬灭。这说明连接位置对荧光淬灭过程有决定性的影响。我们进一步用密度泛函理论(DFT)方法计算和模拟了化合物3-5的结构。化合物3-5中卟啉和三明治之间的空间构型是不同的,3是“交叉型”,而4,5分别是“开贝壳”和“闭贝壳型”。因此连接位置的不同决定了空间构型的不同,进而决定了分子内荧光淬灭过程的不同。3、卟啉修饰的卟啉酞菁混杂三明治化合物中：连接位置决定的荧光淬灭过程研究利用飞秒激光Z扫描技术研究了三种新型的三明治型混杂卟啉酞菁稀土钇双层配合物1-3的三阶非线性光学性质,在三明治型配合物中卟啉一侧的meso-位苯环的邻、间、对位通过酯键分别连接了一个自由卟啉。为了比较研究,也在同样的条件下对参比化合物HY[Pc(α-OC4H9)8](TBPP) (4)进行了测试。这些配合物都显示强的反饱和吸收(RSA)性质,但在飞秒级别的时间范围内遵循RSA-SA-RSA-SA-RSA的变化规律。例如,在光强7.48-8.39 GW·cm-2作用下,对位、间位连接1和2保持RSA的时候,配合物3已经出现了饱和吸收翻转,这表明它们连接位置影响配合物的三阶非线性。4、C60修饰的卟啉酞菁混杂三明治化合物：合成、表征和光物理性质研究一种新型的C60连接的卟啉酞菁混杂三明治化合物被设计、合成和表征。为了合成C60连接的卟啉酞菁混杂三明治化合物首先通过苯醚键在卟啉的meso位上连接C60,然后用这种卟啉和稀土盐[Y(acac)3]·nH2O反应得到半三明治[YⅢ(acac)(Por)] (Por= C60-连接的卟啉；acac=乙酰丙酮),然后再和[1,4,8,11,15,18,22,25-八(丁氧基)酞菁][H2{Pc(α-OC4H9)8}]反应得到目标产物,这种合成路径具有较高的产率。光物理研究显示,在400nm同时激发C60和[HYPcPor]单元,产生从[HYPcPor]到C60的光致电子转移,电荷分离态的寿命可达τ>1 ns。更多还原

【Abstract】 Owing to the unique optical, electrical, and properties, associated with the intriguing intramolecularπ-πinteractions, porphyrins, phthalocyanines, as well as sandwich type rare complexes, as a novel functional materials, have been expected to be widely potential application in materials science, such as in molecular electronics, molecular information storage, and nonlinear optics, etc. Phthalocyanines and porphyrins 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. 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. Due to the intramolecularπ-πinteractions and the intrinsic nature of the metal centers, these novel complexes display characteristic features, which cannot be found in their non-sandwich counterparts, enabling them to be used in different areas. They are versatile materials for electrochromic displays, field effect transistors, gas sensors and as structural and spectroscopic models for the special pair found in the bacterial photosynthetic reaction centers.Due to their fundamental importance in many biological processes, porphyrins (Pors) have been extensively studied in view of biomimetic synthetic models over the past few decades. So, in this paper, we described the synthesis of a series of new Pors and Mixed (Phthalocyaninato)(porphyrinato) Yttrium(III) Double-decker Complexes with novel photophysical properties. Our research work has been focused on the synthesis, characterization, optical properties, and photophysical properties of these macrocyclic tetrapyrrole compounds include the following four parts:1. Synthesis, Electrochemical and Spectroscopic Properties of C60-Porphyrin Dyads with Different Phenyl Ether LinkageA series of C60-porphyrin dyads, connected by phenyl ether linkage of one meso-phenyl group of the porphyrin moiety on para, meta, and ortho positions, respectively, together with their zinc complexes have been designed and synthesized. All of these compounds were characterized by means of MALDI-TOF mass spectrometry, elemental analysis, and 1H NMR. The electronic absorption spectroscopic and electrochemical studies show that there is a considerable interaction between the two chromophores in the ground state of these dyads. The fluorescence spectroscopic study reveals that the emission of porphyrin moiety is efficiently quenched by C60 moiety, and the quenching efficiency is higher when the C60 linked at the ortho position of meso-phenyl ring than that linked at para or meta positions, indicating the linkage dependence of the intramolecular interaction between the two chromophores in these dyads.2. Linkage Dependence of Intramolecular Fluorescence Quenching Process in Porphyrin-appended Mixed (Phthalocyaninato)(porphyrinato) Yttrium(III) Double-decker ComplexesThree novel mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes appended with one metal free porphyrin chromophore at the para, meta, and ortho position, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker unit through ester linkage,3-5, have been designed, synthesized, and spectroscopically characterized. The photophysical properties of these three isomeric tetrapyrrole triads were comparatively investigated along with the model compounds metal free tetra(4-butyl)porphyrin H2TBPP (1) and mixed [1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyaninato] [tetra(4-butyl)-porphyrinato] yttrium double-decker complex HY[Pc(a-OC4H9)g](TBPP) (2) by steady-state and transient spectroscopic methods. The fluorescence of the metal free porphyrin moiety attached through ester linkage at the meta and ortho position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triads 4 and 5 is effectively quenched by the double-decker unit, which takes place in several hundred femtoseconds. However, the fluorescence of the metal free porphyrin moiety attached at the para position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triad 3 is only partially quenched, clearly revealing the effect of the position of porphyrin-substituent on the photophysical properties of the triads. Furthermore, the molecular structures of 3-5 were simulated using density functional theory (DFT) calculations. It was found that the relative orientation between the metal free porphyrin moiety and the double-decker unit for compound 3 is crossed, while those for compounds 4 and 5 are open- and closed-shellfish-like, respectively, which is suggested to be responsible for their different intramolecular fluorescent quenching efficiency. 3. Porphyrin Porphyrin-appended Mixed (Phthalocyaninato)(porphyrinato) Yttrium(Ⅲ) Double-decker Complexes:Effect of Connecting Position of Nonlinear Optical PropertiesThree novel mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes appended with one metal free porphyrin chromophore at the para, meta, and ortho position, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker unit through ester linkage,1-3, as well as mixed [1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyaninato][tetra(4-butyl)-porphyrinato] yttrium double-decker complex HY[Pc(α-OC4H9)8](TBPP) (4) have been investigated by the open-aperture fs Z-scan technique. The third-order nonlinear optical (NLO) properties of these tetrapyrrole triads reveal their strong RSA properties with the nonlinear absorption shifting in the trace of RSA-SA-RSA-SA-RSA at femtosecond timescale. Interestingly, at the intensity of 7.48-8.39 GW/cm2 the triads 1 and 2 with a metal free porphyrin chromophore appended at the para and meta position, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker unit still remain at a characteristic response of RSA. In contrast, the triad 3 with a metal free porphyrin chromophore appended at the ortho position has already shown a trend of SA peak at the same intensity range, confirming the effect of the position of porphyrin-substituent on the photopysical properties of the triads..4. C60-modified Mixed (Phthalocyaninato)(porphyrinato) Yttrium(Ⅲ) Double-decker Complex:Synthesis, Characterization, and Photophysical PropertiesA novel mixed (phthalocyaninato)(porphyrinato) yttrium(Ⅲ) double-decker complex covalently linked with C60 chromophore at the para position of one meso-phenyl group of the porphyrin ligand by phenyl ether linkage has been designed and synthesized by treatment of the half-sandwich yttrium complex [YⅢ(acac)(Por)], generated in situ from [Y(acac)3]·nH2O (acac=acetylacetonate) and the C60-appended free base porphyrin (3), with 1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyanine under reflux in TCB in good yield. The photophysical properties of this novel dyad containing the C60 and mixed (phthalocyaninato)(porphyrinato) yttrium(Ⅲ) double-decker components were investigated by steady-state and transient spectroscopic methods. Comparative studies over the electronic absorption spectra document that there is no considerable electronic interaction between the C60 and mixed (phthalocyaninato)(porphyrinato) yttrium(Ⅲ) double-decker components in steady-state. Time-resolved absorption spectra of this dyad reveal a photoinduced electron transfer from the {HY[Pc(α-OC4H9)g](Por)} to C60 moiety upon irradiation at 400 nm, which excites both C60 and {HY[Pc(α-OC4H9)8](Por)} components, resulting in a charge-separated state with a lifetime longer than 1 ns.更多还原