本文選題：雙自由基　切入點(diǎn)：弱配位陰離子　出處：《南京大學(xué)》2017年碩士論文

【摘要】：雙自由基是指分子中含有兩個(gè)弱相互作用的未成對(duì)電子的化合物。其中含氮雙自由基有著多樣的光、電、磁學(xué)性質(zhì),在高密度信息存儲(chǔ)材料、電子器件、分子磁體、鋰離子電池、光電材料等領(lǐng)域有著巨大的應(yīng)用潛力。近年來它受到了研究者們的廣泛關(guān)注。本論文利用利用弱配位陰離子,設(shè)計(jì)合成了一系列不同橋聯(lián)基團(tuán)的含氮雙陽離子雙自由基,結(jié)合理論計(jì)算對(duì)其結(jié)構(gòu)和性質(zhì)進(jìn)行了詳盡的研究,為構(gòu)筑具有新型結(jié)構(gòu)和性質(zhì)的雙自由基化合物提供了設(shè)計(jì)思路。本論文的主要工作列舉如下:一、合成了一系列萘環(huán)和蒽環(huán)橋聯(lián)的雙三芳胺化合物1-5,并利用弱配位陰離子[A1(ORF)_4]~-(ORF = OC(CF_3)_3)成功穩(wěn)定和分離了四例以萘為橋聯(lián)基團(tuán)的雙胺雙陽離子雙自由基1~(2+)·2[A1(ORF)_4]~--4~(2+)·2[A1(ORF)_4]~-和一例四芳基鄰蒽二胺雙陽離子雙自由基5~(2+)·2[A1(ORF)_4]~-,通過各種實(shí)驗(yàn)表征手段,結(jié)合DFT計(jì)算,研究了它們的幾何結(jié)構(gòu)和電子結(jié)構(gòu)性質(zhì)。對(duì)于具有Kekule構(gòu)型的雙自由基化合物1~(2+)(1,5位取代萘環(huán)的雙(二芳基胺)雙陽離子)和2~(2+)(2,6位取代萘環(huán)的雙(二芳基胺)雙陽離子),基態(tài)均為閉殼層單線態(tài)。3~(2+)(2,7位取代萘環(huán)的雙(二芳基胺)雙陽離子)基態(tài)三線態(tài)分子,而分別以萘和蒽為橋聯(lián)基團(tuán)的Kekule型化合物4~(2+)(1,2位取代萘環(huán)的雙(二芳基胺)雙陽離子)和5~(2+)(1,2位取代蒽環(huán)的雙(二芳基胺)雙陽離子)具有非Kekule式雙自由基性質(zhì),基態(tài)表現(xiàn)出了較大的雙自由基性質(zhì),4~(2+)的基態(tài)為開殼層單線態(tài)。我們的工作進(jìn)一步完善了以萘環(huán)和蒽環(huán)為橋聯(lián)基團(tuán)的Kekule式和非Kekule式雙自由基體系。二、利用雙自由基理念合成了一系列在長(zhǎng)波長(zhǎng)處(通信窗口波段)具有較強(qiáng)近紅外吸收的有機(jī)染料分子。本文成功得到了一系列不同端基取代基的雙三芳胺的BODIPY雙自由基雙陽離子化合物6~(2+)-10~(2+),紫外可見近紅外光譜表明它們的CH2C12溶液分別在1556、1274、1068、1298和1220nm有一較強(qiáng)的近紅外吸收峰。我們可通過調(diào)節(jié)BODIPY母核2,6位取代基團(tuán)端基電負(fù)性獲取不同波長(zhǎng)的近紅外吸收染料分子。這項(xiàng)工作為1300 nm的光學(xué)通信領(lǐng)域提供了一類新的潛在材料,并且為使用雙自由基概念制備近紅外吸收染料提供了指導(dǎo)。
[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.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621

【相似文獻(xiàn)】

相關(guān)期刊論文 前6條

1 楊小兵,丁松濤,王安邦,楊裕生;一種新型方酸菁近紅外吸收染料的合成研究[J];染料工業(yè);2002年06期

2 陳麗媛;陳曉健;孫健;沈永嘉;;近紅外吸收染料的應(yīng)用進(jìn)展[J];染料與染色;2013年06期

3 陳永杰;尚洋洋;張文秀;張靜;耿秀娟;谷亨達(dá);;四-(3,4-二甲氧基苯基)硫代雙烯合鎳的合成與光譜性能[J];精細(xì)化工;2010年11期

4 王寅，，程侶柏;雙齒配位體金屬絡(luò)合物近紅外吸收染料的合成[J];大連理工大學(xué)學(xué)報(bào);1995年04期

5 王茜;鄭文偉;程海峰;門金鳳;楚增勇;;硫代雙烯型金屬配合物近紅外染料研究進(jìn)展[J];材料導(dǎo)報(bào);2007年01期

6 ;[J];;年期

相關(guān)碩士學(xué)位論文 前6條

1 魏厚佳;雙（三芳胺）雙自由基的合成及其近紅外吸收性質(zhì)的研究[D];南京大學(xué);2017年

2 王鳳云;方酸菁近紅外吸收染料的合成及其光譜性質(zhì)的研究[D];長(zhǎng)春理工大學(xué);2010年

3 董霆;不對(duì)稱硫代雙烯型金屬配合物的制備及光譜性能研究[D];長(zhǎng)春理工大學(xué);2010年

4 陳進(jìn)明;硫代雙烯型金屬配合物的合成及其光譜性質(zhì)的研究[D];長(zhǎng)春理工大學(xué);2009年

5 王茜;硫代雙烯型鎳配合物的合成及性能研究[D];國(guó)防科學(xué)技術(shù)大學(xué);2007年

6 楊晶晶;胺鹽類化合物的合成及其防激光性能的研究[D];長(zhǎng)春理工大學(xué);2007年

本文編號(hào)：1669554