【摘要】：光合作用巧妙的將自然界中的太陽能轉化成化學能,而光誘導的電荷轉移成為這一轉化的關鍵。因此,可以通過構建多元體系產生多步光誘導的電荷轉移,進行人工模擬光合作用。富勒烯C_(60)分子不僅具有對稱的全碳分子結構,還具有較高的電子親和力、合適的還原電勢、較低的重組能等特點,使得其能夠作為良好的電子或能量受體。富勒烯C_(60)及其衍生物作為受體在光誘導電荷轉移的研究方面具有著不可或缺的作用。本文構建了基于富勒烯的D-A型給受體體系,并在此基礎上,按照一定的氧化還原梯度,增加發(fā)色基團或引入次級電子給體,構建了多個剛性的、多元的D-A型體系,以獲得較長壽命的電荷分離態(tài)。本文進行的研究有望為富勒烯多元體系在光電器件中的應用提供必要的理論及實驗支持。本論文主要進行了以下幾個方面的研究:1.富勒烯二元體系的制備:本文首先以苯甲醛、3-羥基苯甲醛、吡咯等為原料制備了卟啉、金屬(Ni、Cu、Pt)卟啉化合物。然后通過Bingel反應將金屬卟啉與C_(60)連接組成六種不同的金屬卟啉-C_(60)的二元體系,并對產物進行了高分辨質譜、核磁共振氫譜、碳譜等表征。2.含金屬的富勒烯三元體系的制備:本文以苯甲醛、對羥基苯甲醛、吡咯、C_(60)等為原料,依次經并以Lindsey消除、烷基化、親核取代、Prato環(huán)加成等方法,合成了含金屬銅的BDP-TPP-C_(60)三元體系,并對產物進行高分辨質譜等表征。另外,以聯(lián)二吡啶衍生物、聚噻吩衍生物、C_(60)等為原料,依次經親核取代、Prato環(huán)加成反應制備了 bpy-4T-C_(60)三元體系。并將該三元體系與金屬Cu離子配位,構建了含金屬銅的bpy-4T-C_(60)三元體系。3.不含金屬的富勒烯三元體系的制備:本文以2-噻吩甲腈、丁二酸二丁酯、C_(60)等為原料,依次經縮合、烷基化、溴化、Suzuki偶聯(lián)、Prato反應等方法成功合成了 TPA-TDPPT-C_(60)三元體系化合物,并對產物進行了高分辨質譜、核磁共振氫譜等表征。另外,以氟硼二吡咯衍生物、三芳基胺硼酸、C_(60)等為原料,通過Vilsmeier反應、溴代、Suzuki偶聯(lián)、Prato反應等方法成功合成了 TPA-TBDPT-C_(60)三元體系,并對產物進行了核磁共振氫譜、紫外光譜等表征。這些工作進一步豐富了富勒烯多元體系的種類,為實現長壽命的電荷分離態(tài)提供了備選化合物。
[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.
【學位授予單位】：天津工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O613.71

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