【摘要】：具有D-π-A結(jié)構(gòu)的碳硼烷化合物由于其立體的芳香性、獨特的物理化學性質(zhì)以及較高的化學熱穩(wěn)定性,在分子電池、非線性光學、光電材料等領(lǐng)域受到越來越多的關(guān)注。本課題主要基于鄰位碳硼烷,設(shè)計合成了一系列鄰位碳硼烷化合物,并且研究其獨特的光學性質(zhì)�？偟膩碇v,本論文的工作主要分為兩個部分:線性光學性質(zhì)的研究(特別是固體熒光的研究)和非線性光學性質(zhì)的研究(主要涉及在三階非線性光學性質(zhì)方面的研究并完成了相關(guān)化合物合成與表征工作)。在第二章中,主要重點研究了含芴基碳硼烷化合物的固體熒光性質(zhì)。本章通過炔烴與B10H12((C2H5)S)2合成了一組單取代和雙取代含芴基的鄰位碳硼烷化合物(Fl-Cb),產(chǎn)率在60%左右。其中,雙取代化合物的晶體結(jié)構(gòu)顯示該類化合物存在具有較為剛性的“head-to-tail”或者“tail-to-tail”堆積方式,然而在單取代化合物中只發(fā)現(xiàn)比較脆弱的堆積方式。在溶液中,這些化合物(Fl-Cb)表現(xiàn)出嚴重的熒光猝滅并在混合溶劑中獲得的發(fā)光聚集體的熒光量子產(chǎn)率大約在0.11左右。然而,在雙取代化合物中觀察到的晶體誘導發(fā)光的熒光量子產(chǎn)率最高達到0.95。除了具有較寬的發(fā)射光譜以外,這些化合物的激發(fā)光譜的范圍也很寬,這表明化合物在晶體態(tài)下存在軌道簡并。理論計算也證實了分子內(nèi)在的軌道簡并與高度有序的晶體結(jié)構(gòu)是引起這些化合物顯著晶體誘導發(fā)光的主要原因。在第三章中,主要重點研究了鄰位碳硼烷化合物在三階非線性光學領(lǐng)域的應(yīng)用。本章主要通過Sornogashira偶聯(lián)反應(yīng)以及脫甲硅基反應(yīng)合成了一系列具有“Z”字型結(jié)構(gòu),且有不同供電子能力基團的碳硼烷化合物c1、c2、c3、c4、c5。上述化合物均采用核磁共振(氫譜、碳譜和硼譜)、質(zhì)譜、全反射傅立葉紅外光譜、元素分析對分子結(jié)構(gòu)和純度進行驗證。
[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.
【學位授予單位】：江南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O627.31

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