富勒烯的二、三元体系的设计合成及性能研究
发布时间：2018-10-30 14:49
【摘要】：光合作用巧妙的将自然界中的太阳能转化成化学能,而光诱导的电荷转移成为这一转化的关键。因此,可以通过构建多元体系产生多步光诱导的电荷转移,进行人工模拟光合作用。富勒烯C_(60)分子不仅具有对称的全碳分子结构,还具有较高的电子亲和力、合适的还原电势、较低的重组能等特点,使得其能够作为良好的电子或能量受体。富勒烯C_(60)及其衍生物作为受体在光诱导电荷转移的研究方面具有着不可或缺的作用。本文构建了基于富勒烯的D-A型给受体体系,并在此基础上,按照一定的氧化还原梯度,增加发色基团或引入次级电子给体,构建了多个刚性的、多元的D-A型体系,以获得较长寿命的电荷分离态。本文进行的研究有望为富勒烯多元体系在光电器件中的应用提供必要的理论及实验支持。本论文主要进行了以下几个方面的研究:1.富勒烯二元体系的制备:本文首先以苯甲醛、3-羟基苯甲醛、吡咯等为原料制备了卟啉、金属(Ni、Cu、Pt)卟啉化合物。然后通过Bingel反应将金属卟啉与C_(60)连接组成六种不同的金属卟啉-C_(60)的二元体系,并对产物进行了高分辨质谱、核磁共振氢谱、碳谱等表征。2.含金属的富勒烯三元体系的制备:本文以苯甲醛、对羟基苯甲醛、吡咯、C_(60)等为原料,依次经并以Lindsey消除、烷基化、亲核取代、Prato环加成等方法,合成了含金属铜的BDP-TPP-C_(60)三元体系,并对产物进行高分辨质谱等表征。另外,以联二吡啶衍生物、聚噻吩衍生物、C_(60)等为原料,依次经亲核取代、Prato环加成反应制备了 bpy-4T-C_(60)三元体系。并将该三元体系与金属Cu离子配位,构建了含金属铜的bpy-4T-C_(60)三元体系。3.不含金属的富勒烯三元体系的制备:本文以2-噻吩甲腈、丁二酸二丁酯、C_(60)等为原料,依次经缩合、烷基化、溴化、Suzuki偶联、Prato反应等方法成功合成了 TPA-TDPPT-C_(60)三元体系化合物,并对产物进行了高分辨质谱、核磁共振氢谱等表征。另外,以氟硼二吡咯衍生物、三芳基胺硼酸、C_(60)等为原料,通过Vilsmeier反应、溴代、Suzuki偶联、Prato反应等方法成功合成了 TPA-TBDPT-C_(60)三元体系,并对产物进行了核磁共振氢谱、紫外光谱等表征。这些工作进一步丰富了富勒烯多元体系的种类,为实现长寿命的电荷分离态提供了备选化合物。
[Abstract]:Photosynthesis cleverly converts solar energy from nature into chemical energy, and photoinduced charge transfer is the key to this transformation. Therefore, multistep photoinduced charge transfer can be generated by constructing a multicomponent system, and photosynthesis can be simulated artificially. Fullerene C _ (60) has not only symmetrical total carbon structure, but also high electron affinity, suitable reduction potential and low recombination energy, which makes it a good electron or energy receptor. Fullerene C _ (60) and its derivatives as receptors play an indispensable role in the study of photoinduced charge transfer. In this paper, the D-A type donor system based on fullerene is constructed, and on the basis of this, according to a certain redox gradient, the chromogenic group is added or secondary electron donor is introduced, and several rigid, multivariate D-A type systems are constructed. In order to obtain long lifetime charge separation state. The research in this paper is expected to provide the necessary theoretical and experimental support for the application of fullerene in optoelectronic devices. This paper mainly carries on the following aspects of research: 1. Preparation of fullerene binary system: firstly, porphyrin, metal (Ni,Cu,Pt) porphyrin compounds were prepared from benzaldehyde, 3-hydroxybenzaldehyde and pyrrole. Six different binary systems of metalloporphyrin-C _ (60) were formed by Bingel reaction. The products were characterized by high resolution mass spectrometry, nuclear magnetic resonance (NMR) and carbon spectroscopy. 2. Preparation of metal-containing fullerene ternary system: in this paper, benzaldehyde, p-hydroxybenzaldehyde, pyrrole, C60 were used as raw materials, followed by Lindsey elimination, alkylation, nucleophilic substitution, Prato cycloaddition, etc. BDP-TPP-C_ (60) ternary system containing metal copper was synthesized and characterized by high resolution mass spectrometry. In addition, bpy-4T-C_ _ (60) ternary system was prepared by nucleophilic substitution from bipyridine derivatives, polythiophene derivatives, C60 derivatives and Prato cycloaddition reaction. The bpy-4T-C_ _ (60) ternary system containing metal copper was constructed by the coordination of the ternary system with metal Cu ion. Preparation of metal-free fullerene ternary system: in this paper, 2-thiophenonitrile, dibutyl succinate and C60 were used as raw materials, followed by condensation, alkylation, bromination, Suzuki coupling, etc. TPA-TDPPT-C_ (60) ternary compounds were synthesized by Prato reaction and characterized by high resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR). In addition, the ternary system of TPA-TBDPT-C_ (60) was successfully synthesized by Vilsmeier reaction, bromination, Suzuki coupling and Prato reaction with fluoroborborate dipyrrole derivative, triaryl amine boric acid and C60 as raw materials. The products were characterized by NMR and UV spectra. These works further enrich the variety of fullerene multicomponent systems and provide alternative compounds for long lifetime charge separation.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O613.71
[Abstract]:Photosynthesis cleverly converts solar energy from nature into chemical energy, and photoinduced charge transfer is the key to this transformation. Therefore, multistep photoinduced charge transfer can be generated by constructing a multicomponent system, and photosynthesis can be simulated artificially. Fullerene C _ (60) has not only symmetrical total carbon structure, but also high electron affinity, suitable reduction potential and low recombination energy, which makes it a good electron or energy receptor. Fullerene C _ (60) and its derivatives as receptors play an indispensable role in the study of photoinduced charge transfer. In this paper, the D-A type donor system based on fullerene is constructed, and on the basis of this, according to a certain redox gradient, the chromogenic group is added or secondary electron donor is introduced, and several rigid, multivariate D-A type systems are constructed. In order to obtain long lifetime charge separation state. The research in this paper is expected to provide the necessary theoretical and experimental support for the application of fullerene in optoelectronic devices. This paper mainly carries on the following aspects of research: 1. Preparation of fullerene binary system: firstly, porphyrin, metal (Ni,Cu,Pt) porphyrin compounds were prepared from benzaldehyde, 3-hydroxybenzaldehyde and pyrrole. Six different binary systems of metalloporphyrin-C _ (60) were formed by Bingel reaction. The products were characterized by high resolution mass spectrometry, nuclear magnetic resonance (NMR) and carbon spectroscopy. 2. Preparation of metal-containing fullerene ternary system: in this paper, benzaldehyde, p-hydroxybenzaldehyde, pyrrole, C60 were used as raw materials, followed by Lindsey elimination, alkylation, nucleophilic substitution, Prato cycloaddition, etc. BDP-TPP-C_ (60) ternary system containing metal copper was synthesized and characterized by high resolution mass spectrometry. In addition, bpy-4T-C_ _ (60) ternary system was prepared by nucleophilic substitution from bipyridine derivatives, polythiophene derivatives, C60 derivatives and Prato cycloaddition reaction. The bpy-4T-C_ _ (60) ternary system containing metal copper was constructed by the coordination of the ternary system with metal Cu ion. Preparation of metal-free fullerene ternary system: in this paper, 2-thiophenonitrile, dibutyl succinate and C60 were used as raw materials, followed by condensation, alkylation, bromination, Suzuki coupling, etc. TPA-TDPPT-C_ (60) ternary compounds were synthesized by Prato reaction and characterized by high resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR). In addition, the ternary system of TPA-TBDPT-C_ (60) was successfully synthesized by Vilsmeier reaction, bromination, Suzuki coupling and Prato reaction with fluoroborborate dipyrrole derivative, triaryl amine boric acid and C60 as raw materials. The products were characterized by NMR and UV spectra. These works further enrich the variety of fullerene multicomponent systems and provide alternative compounds for long lifetime charge separation.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O613.71
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