具有光电功能的四吡啶卟啉电荷转移化合物的研究

发布时间：2018-05-25 09:14

本文选题：卟啉 + 四硫富瓦烯羧酸　；参考：《苏州大学》2016年硕士论文

【摘要】：卟啉化合物在自然界中广泛存在,由于它具有独特的结构、性能和特殊的生物活性,所以在材料化学、医学、生物化学、合成化学、分析化学、能源利用等方面有着很好的应用前景。卟啉和金属卟啉化合物在D-A化合物中通常充当电子给体。可以通过引入强的吸电子基团,高价的金属离子和质子到卟啉化合物中作为电子受体来调控化合物的性质。四硫富瓦烯(TTF)及其衍生物由于具有良好的供电子能力和氧化还原性质,一直备受关注,在很多领域都有着十分重要的应用,如在超分子化学、导体、半导体、超导体材料、生物传感器以及化学传感器等方面。锗硫属化合物不仅在催化、离子交换等方面有很好的应用价值,还因其独特的光电性能,在半导体、非线性光学等方面具有广泛的应用前景。本文以四吡啶卟啉为研究对象,将TTF和(Ge4S10)4-引入到卟啉体系中并得到了四吡啶卟啉和过渡金属Mn(II)的配合物。主要包括以下内容:一、绪论部分简要介绍了卟啉衍生物的性质及研究现状,综述了卟啉及其衍生物在光电材料和能源利用领域的应用。介绍了TTF及其衍生物在分子器件和光电转换材料领域的研究进展。此外,还阐述了电荷转移化合物的独特性质及其在光电领域的应用。最后,介绍了本论文的研究意义以及主要研究内容。二、合成了基于TTF-二羧酸(L1)、TTF-四羧酸(L2)作为阴离子和(TMPy P)4+作为阳离子构建的{[cation]n+·[TTFs]n }型电荷转移盐:{TMPy P-(HL1)4}?3H2O(1)和{TMPy P-(H2L2)2}?5H2O(2)。两种化合物晶体结构都呈DDADDA的有序堆积。通过对化合物UV vis,ESR以及荧光性质的测试,并结合化合物的晶体结构,研究了这两种化合物的电荷转移现象。研究发现化合物1的电荷转移作用比化合物2强。解释了电荷转移作用与分子堆积结构的关系。该阴阳离子型的的电荷转移化合物还具有很好的光电响应能力。另外,阐述了产生光电流的机理。三、将功能性阴离子(Ge4S10)4-引入到卟啉体系中得到了化合物{TMPy P-Ge4S10}?3H2O(3)。化合物3的晶体结构表明阴离子(Ge4S10)4-层被夹在上下两层阳离子(TMPy P)4+之间形成了三明治的结构,UV vis图谱中可以观察到明显的电荷转移吸收峰。该化合物的晶体具有光电响应性质。除此之外,我们把过渡金属锰离子及桥连Cl离子引入到四吡啶卟啉(Py P)体系中得到了化合物[Mn2(Py P)Cl3]?CHCl3?H2O(4)。晶体结构分析表明化合物4具有双层二维结构。光谱研究发现,由于分子间的能量转移导致Py P的荧光发生了淬灭。
[Abstract]:Porphyrin compounds are widely found in nature. Because of their unique structure, properties and special biological activities, porphyrin compounds are widely used in materials chemistry, medicine, biochemistry, synthetic chemistry, analytical chemistry. Energy utilization and other aspects have a good application prospects. Porphyrins and metalloporphyrins usually act as electron donors in D-A compounds. The properties of the compounds can be regulated by the introduction of strong electron-absorbing groups, high valence metal ions and protons into porphyrin compounds as electron receptors. Tetrathiafurane (TTF) and its derivatives have attracted much attention due to their good electron supply and redox properties, and have been widely used in many fields, such as supramolecular chemistry, conductors, semiconductors and superconductor materials. Biosensors and chemical sensors and so on. Germanium and sulfur compounds not only have good application value in catalysis, ion exchange and so on, but also have wide application prospects in semiconductor, nonlinear optics and so on because of their unique photoelectric properties. In this paper, tetrapyridine-porphyrin was used as the study object, TTF and Ge4S104- were introduced into porphyrin system and the complexes of tetrapyridine-porphyrin and transition metal Mn-II were obtained. The main contents are as follows: 1. In the introduction, the properties and research status of porphyrin derivatives are briefly introduced, and the applications of porphyrins and their derivatives in the field of optoelectronic materials and energy utilization are reviewed. The research progress of TTF and its derivatives in molecular devices and optoelectronic conversion materials are reviewed. In addition, the unique properties of charge transfer compounds and their applications in the field of photoelectricity are also described. Finally, the research significance and main research contents of this paper are introduced. Secondly, the {[cation] n [TTFs] n (cation) and {TMPy P-(H2L2)2} (3H _ 2O _ 2) and {TMPy P-(H2L2)2} ~ (5) H _ 2O _ 2 were synthesized based on TTF-dicarboxylic acid (TTF-dicarboxylic acid) as anion and TMPy Pn4 as cationic ions. The crystal structure of the two compounds is ordered stacking of DDADDA. The charge transfer phenomena of the two compounds were studied by measuring the ESR and fluorescence properties of the compounds and combining with the crystal structure of the compounds. It was found that the charge transfer effect of compound 1 was stronger than that of compound 2. The relationship between charge transfer and molecular stacking structure is explained. The cationic charge transfer compound also has good photoelectric response ability. In addition, the mechanism of photocurrent generation is described. Thirdly, the functional anion Ge4S10O4- was introduced into porphyrin system to obtain the compound {TMPy P-Ge4S10} 3 H 2O 3. The crystal structure of compound 3 indicates that the structure of the sandwich is formed between the upper and lower layers of the anionic GE _ 4S _ (10) O _ (4-) _ 4 layer, and the obvious charge-transfer absorption peaks can be observed in the vis spectra of the sandwich. The crystal of the compound has the property of photoelectric response. In addition, the transition metal manganese ion and bridged Cl ion were introduced into the system of tetrapyridine porphyrin (Py P) to obtain the compound [Mn2(Py P)Cl3] CHCl _ 3H _ 2O _ 4. The crystal structure analysis shows that compound 4 has a two-layer two-dimensional structure. It is found that the fluorescence of Py P is quenched due to the energy transfer between molecules.
【学位授予单位】：苏州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

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