邻位碳硼烷衍生物的合成及其光学性质的研究
发布时间：2019-03-26 17:24
【摘要】：具有D-π-A结构的碳硼烷化合物由于其立体的芳香性、独特的物理化学性质以及较高的化学热稳定性,在分子电池、非线性光学、光电材料等领域受到越来越多的关注。本课题主要基于邻位碳硼烷,设计合成了一系列邻位碳硼烷化合物,并且研究其独特的光学性质。总的来讲,本论文的工作主要分为两个部分:线性光学性质的研究(特别是固体荧光的研究)和非线性光学性质的研究(主要涉及在三阶非线性光学性质方面的研究并完成了相关化合物合成与表征工作)。在第二章中,主要重点研究了含芴基碳硼烷化合物的固体荧光性质。本章通过炔烃与B10H12((C2H5)S)2合成了一组单取代和双取代含芴基的邻位碳硼烷化合物(Fl-Cb),产率在60%左右。其中,双取代化合物的晶体结构显示该类化合物存在具有较为刚性的“head-to-tail”或者“tail-to-tail”堆积方式,然而在单取代化合物中只发现比较脆弱的堆积方式。在溶液中,这些化合物(Fl-Cb)表现出严重的荧光猝灭并在混合溶剂中获得的发光聚集体的荧光量子产率大约在0.11左右。然而,在双取代化合物中观察到的晶体诱导发光的荧光量子产率最高达到0.95。除了具有较宽的发射光谱以外,这些化合物的激发光谱的范围也很宽,这表明化合物在晶体态下存在轨道简并。理论计算也证实了分子内在的轨道简并与高度有序的晶体结构是引起这些化合物显著晶体诱导发光的主要原因。在第三章中,主要重点研究了邻位碳硼烷化合物在三阶非线性光学领域的应用。本章主要通过Sornogashira偶联反应以及脱甲硅基反应合成了一系列具有“Z”字型结构,且有不同供电子能力基团的碳硼烷化合物c1、c2、c3、c4、c5。上述化合物均采用核磁共振(氢谱、碳谱和硼谱)、质谱、全反射傅立叶红外光谱、元素分析对分子结构和纯度进行验证。
[Abstract]:Carbon borane compounds with D-蟺-A structure have attracted more and more attention in the fields of molecular batteries, nonlinear optics, photoelectric materials and so on because of their three-dimensional aromaticity, unique physical and chemical properties and high chemical thermal stability. In this paper, a series of ortho-carbon borane compounds have been designed and synthesized based on ortho-carbon borane, and their unique optical properties have been studied. In general, The main work of this thesis is divided into two parts: the study of linear optical properties (especially the study of solid-state fluorescence) and the study of nonlinear optical properties (mainly related to the study of third-order nonlinear optical properties) and the completion of the study. The synthesis and characterization of related compounds were studied. In the second chapter, the solid fluorescence properties of fluorene-containing carbon borane compounds are mainly studied. In this chapter, a group of monosubstituted and disubstituted ortho-fluorenyl compounds (Fl-Cb) were synthesized from alkynes and B10H12 (C2H5) S) 2) with yields of about 60%. Among them, the crystal structure of disubstituted compounds shows that these compounds have rigid "head-to-tail" or "tail-to-tail" stacking modes, but only fragile stacking modes are found in monosubstituted compounds. In the solution, these compounds (Fl-Cb) exhibit severe fluorescence quenching and the fluorescence quantum yields of the luminescent aggregates obtained in mixed solvents are about 0.11. However, the fluorescence quantum yield of crystal-induced luminescence observed in disubstituted compounds was up to 0.95. In addition to the wide emission spectra, the excitation spectra of these compounds are also very wide, which indicates the existence of orbital degeneracy in the crystalline state of the compounds. Theoretical calculations also confirm that the intrinsic orbital degeneracy and highly ordered crystal structure of the molecules are the main reasons for the significant crystal-induced luminescence of these compounds. In chapter 3, the application of ortho-carbon borane in third-order nonlinear optics is mainly studied. In this chapter, Sornogashira coupling reaction and demethylsilyl reaction were used to synthesize a series of carbon borane compounds with "Z"-shaped structure and different electron donor groups, such as c _ 1, C _ 2, C _ 3, C _ 4, C _ 5, and C _ 1, C _ 2, C _ 3, C _ 4 and C _ 5. The molecular structure and purity of the compounds were verified by NMR (hydrogen spectrum, carbon spectrum and boron spectrum), mass spectrometry, total reflection Fourier transform infrared spectroscopy (TFT-IR) and elemental analysis.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O627.31
[Abstract]:Carbon borane compounds with D-蟺-A structure have attracted more and more attention in the fields of molecular batteries, nonlinear optics, photoelectric materials and so on because of their three-dimensional aromaticity, unique physical and chemical properties and high chemical thermal stability. In this paper, a series of ortho-carbon borane compounds have been designed and synthesized based on ortho-carbon borane, and their unique optical properties have been studied. In general, The main work of this thesis is divided into two parts: the study of linear optical properties (especially the study of solid-state fluorescence) and the study of nonlinear optical properties (mainly related to the study of third-order nonlinear optical properties) and the completion of the study. The synthesis and characterization of related compounds were studied. In the second chapter, the solid fluorescence properties of fluorene-containing carbon borane compounds are mainly studied. In this chapter, a group of monosubstituted and disubstituted ortho-fluorenyl compounds (Fl-Cb) were synthesized from alkynes and B10H12 (C2H5) S) 2) with yields of about 60%. Among them, the crystal structure of disubstituted compounds shows that these compounds have rigid "head-to-tail" or "tail-to-tail" stacking modes, but only fragile stacking modes are found in monosubstituted compounds. In the solution, these compounds (Fl-Cb) exhibit severe fluorescence quenching and the fluorescence quantum yields of the luminescent aggregates obtained in mixed solvents are about 0.11. However, the fluorescence quantum yield of crystal-induced luminescence observed in disubstituted compounds was up to 0.95. In addition to the wide emission spectra, the excitation spectra of these compounds are also very wide, which indicates the existence of orbital degeneracy in the crystalline state of the compounds. Theoretical calculations also confirm that the intrinsic orbital degeneracy and highly ordered crystal structure of the molecules are the main reasons for the significant crystal-induced luminescence of these compounds. In chapter 3, the application of ortho-carbon borane in third-order nonlinear optics is mainly studied. In this chapter, Sornogashira coupling reaction and demethylsilyl reaction were used to synthesize a series of carbon borane compounds with "Z"-shaped structure and different electron donor groups, such as c _ 1, C _ 2, C _ 3, C _ 4, C _ 5, and C _ 1, C _ 2, C _ 3, C _ 4 and C _ 5. The molecular structure and purity of the compounds were verified by NMR (hydrogen spectrum, carbon spectrum and boron spectrum), mass spectrometry, total reflection Fourier transform infrared spectroscopy (TFT-IR) and elemental analysis.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O627.31
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