双（三芳胺）双自由基的合成及其近红外吸收性质的研究

发布时间：2018-03-26 21:00

本文选题：双自由基　切入点：弱配位阴离子　出处：《南京大学》2017年硕士论文

【摘要】：双自由基是指分子中含有两个弱相互作用的未成对电子的化合物。其中含氮双自由基有着多样的光、电、磁学性质,在高密度信息存储材料、电子器件、分子磁体、锂离子电池、光电材料等领域有着巨大的应用潜力。近年来它受到了研究者们的广泛关注。本论文利用利用弱配位阴离子,设计合成了一系列不同桥联基团的含氮双阳离子双自由基,结合理论计算对其结构和性质进行了详尽的研究,为构筑具有新型结构和性质的双自由基化合物提供了设计思路。本论文的主要工作列举如下:一、合成了一系列萘环和蒽环桥联的双三芳胺化合物1-5,并利用弱配位阴离子[A1(ORF)_4]~-(ORF = OC(CF_3)_3)成功稳定和分离了四例以萘为桥联基团的双胺双阳离子双自由基1~(2+)·2[A1(ORF)_4]~--4~(2+)·2[A1(ORF)_4]~-和一例四芳基邻蒽二胺双阳离子双自由基5~(2+)·2[A1(ORF)_4]~-,通过各种实验表征手段,结合DFT计算,研究了它们的几何结构和电子结构性质。对于具有Kekule构型的双自由基化合物1~(2+)(1,5位取代萘环的双(二芳基胺)双阳离子)和2~(2+)(2,6位取代萘环的双(二芳基胺)双阳离子),基态均为闭壳层单线态。3~(2+)(2,7位取代萘环的双(二芳基胺)双阳离子)基态三线态分子,而分别以萘和蒽为桥联基团的Kekule型化合物4~(2+)(1,2位取代萘环的双(二芳基胺)双阳离子)和5~(2+)(1,2位取代蒽环的双(二芳基胺)双阳离子)具有非Kekule式双自由基性质,基态表现出了较大的双自由基性质,4~(2+)的基态为开壳层单线态。我们的工作进一步完善了以萘环和蒽环为桥联基团的Kekule式和非Kekule式双自由基体系。二、利用双自由基理念合成了一系列在长波长处(通信窗口波段)具有较强近红外吸收的有机染料分子。本文成功得到了一系列不同端基取代基的双三芳胺的BODIPY双自由基双阳离子化合物6~(2+)-10~(2+),紫外可见近红外光谱表明它们的CH2C12溶液分别在1556、1274、1068、1298和1220nm有一较强的近红外吸收峰。我们可通过调节BODIPY母核2,6位取代基团端基电负性获取不同波长的近红外吸收染料分子。这项工作为1300 nm的光学通信领域提供了一类新的潜在材料,并且为使用双自由基概念制备近红外吸收染料提供了指导。
[Abstract]:A double radical is a compound containing two unpaired electrons that interact weakly in a molecule. The nitrogen-containing bisradical has a variety of optical, electrical and magnetic properties, in high density information storage materials, electronic devices, molecular magnets, Lithium ion batteries, optoelectronic materials and other fields have great application potential. In recent years, it has attracted extensive attention of researchers. In this paper, the use of weak coordination anions, A series of nitrogen-containing double cationic double free radicals with different bridging groups were designed and synthesized, and their structures and properties were studied in detail by theoretical calculation. The main work of this paper is as follows: 1. A series of naphthalene and anthracycline bridged bistriarylamine compounds 1-5 were synthesized and successfully stabilized and separated by using weakly coordinated anions [A1(ORF)_4] -orf = OCST-CF3 (3). Four cases of dicarboxylic diamines with naphthalene as bridged groups, diamine cationic dicarboxylamine 2 [A1(ORF)_4] -42) [A1(ORF)_4] 2 [A1(ORF)_4] and a case of Teflon were successfully stabilized and separated. O-anthracene diamine double cationic bisradical 5 ~ (2) [A1(ORF)_4] ~ (-) _ 2, which was characterized by various experimental methods. Combined with DFT calculation, The geometrical and electronic structures of these compounds have been studied. For diarylamines with Kekule configuration, bis (diaryl amines) dications of 5 substituted naphthalene rings and bis (diaryl amines) bis (diaryl amines) of 6 substituted naphthalene rings with Kekule configuration are obtained. The ground state of cationic anion is a closed shell monowire state. 3 ~ (2 +) ~ 2 ~ (2 +) -diarylamine-dication) three-wire molecule, which replaces the naphthalene ring at the 7 ~ (-) ~ (-) ~ (-) ~ (7) position. The Kekule compounds with naphthalene and anthracene as bridged groups, respectively, have the properties of non-#en1# type bis (diaryl amines) and disubstituted dicarboxylamines (diaryl amines), which are substituted by naphthalene and anthracene, respectively, and the bis (diaryl amines) dications, which are substituted by naphthalene and anthracene, respectively. The ground state of the ground state shows a large double free radical property and the ground state is an open-shell singlet state. Our work has further improved the Kekule type and non-#en1# type double radical systems with naphthalene ring and anthracycline as bridged groups. A series of organic dyestuffs with strong near infrared absorption in the long wave band (communication window band) have been synthesized by using the idea of double radical. In this paper, we have successfully obtained a series of BODIPY double self of bistriarylamine with different terminal substituents. The UV-Vis near infrared spectra show that their CH2C12 solution has a strong near infrared absorption peak at 1556 ~ 1274 ~ 1068 ~ 1298 and 1220nm by adjusting the electronegativity of the 6-substituent group in the BODIPY parent nucleus by adjusting the electronegativity of the 6-substituent group in the BODIPY parent nucleus. Near-infrared absorption of dye molecules at different wavelengths. This work provides a new class of potential materials for optical communication at 1300 nm. It also provides guidance for the preparation of near infrared absorption dyes by using the concept of double radical.
【学位授予单位】：南京大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621

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