本文選題：二芳甲基自由基 + 三芳基甲基碳正離子自由基��； 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年碩士論文

【摘要】：本論文主要論述了芳基甲基自由基功能材料的研究進(jìn)展以及質(zhì)子化效應(yīng)在有機(jī)分子中的應(yīng)用。在本實(shí)驗(yàn)室之前的研究工作中,我們合成出一種穩(wěn)定的發(fā)光性的中性自由基底物obip和obip-CHO,在此基礎(chǔ)上,進(jìn)一步拓展功能自由基材料的研究。首先,通過(guò)簡(jiǎn)單的一鍋法設(shè)計(jì)合成了兩種穩(wěn)定新型的二芳甲基單自由基5和二芳甲基三自由基7,兩種自由基由于各自不同的電子結(jié)構(gòu)和堆積狀態(tài),展現(xiàn)出不同的性能。并且5在HC1O4溶液中酸化后,可以容易地轉(zhuǎn)變?yōu)?。跟5相比,7具有更高的量子產(chǎn)率并且近紅外吸收增強(qiáng),這是由于7中存在獨(dú)特的質(zhì)子分享型氫鍵。另外,在酸堿氣體的刺激下,5和7之間的磷光、顏色和磁性性質(zhì)可以互相轉(zhuǎn)換,同時(shí)相應(yīng)地給出不同EPR信號(hào)。因此,質(zhì)子分享型氫鍵可以作為5跟7的開(kāi)關(guān):當(dāng)被質(zhì)子化時(shí),開(kāi)關(guān)"開(kāi)"7穩(wěn)定存在,EPR呈現(xiàn)七重信號(hào)峰,具有熒光性能;當(dāng)去質(zhì)子化,開(kāi)關(guān)"關(guān)"7轉(zhuǎn)變成5,EPR呈現(xiàn)單信號(hào)峰,發(fā)光較弱。7對(duì)酸堿性氣體產(chǎn)生的這種刺激響應(yīng)性能,使其可以被制備成為氨氣的磷光傳感器件。這項(xiàng)工作為研究新的通過(guò)外部刺激可以可逆的轉(zhuǎn)變顏色、發(fā)光、磁性的多功能材料提供一種新型合成方法,以及為制備新型傳感器件提供了靈感。其次,在上一章的研究基礎(chǔ)上,我們又繼續(xù)培養(yǎng)了一種鹽酸體系下的單晶,該晶體中具有通過(guò)多重氫鍵相互作用形成的有趣的三環(huán)式[6.2.0.0]構(gòu)型。此外,我們也根據(jù)單晶的晶體學(xué)證據(jù),首次報(bào)道了一種室溫下未解離的HC1水合物單晶及其水分子二聚體具有的非常規(guī)順式-線性構(gòu)象。也證明了該獨(dú)特現(xiàn)象是由三環(huán)式構(gòu)型的環(huán)幾何效應(yīng)引起的。本章工作的重要性在于探索出室溫下也可以得到未解離的HC1水合物單晶,和沒(méi)有穴腔束縛作用也可以得到順式-線性構(gòu)象的水分子二聚體。我們的工作為室溫下探索HC1-H20體系新型構(gòu)型提供幫助。最后,基于實(shí)驗(yàn)室之前報(bào)道的三種新型的三芳基甲基碳正離子自由基,發(fā)現(xiàn)這三種三芳基甲基碳正離子自由基鹽是同分異構(gòu)體,并且在300 K時(shí)表現(xiàn)出不同的磁化率值。本章通過(guò)簡(jiǎn)單的"一鍋法"合成一種三芳基甲基碳正離子自由基(標(biāo)為T(mén)AM+··Cl-),有趣的是,當(dāng)將其質(zhì)子化后,"cis"TAM+··Cl-轉(zhuǎn)化成"trans"三芳基甲基碳正離子自由基(標(biāo)為HTAM2+··2ClO4-·H2O)。如此明顯的構(gòu)象改變,是由一個(gè)環(huán)外羰基氧原子和被質(zhì)子化的吡啶氮原子形成的分子內(nèi)氫鍵引起的。同時(shí),構(gòu)象的改變也帶來(lái)晶體結(jié)構(gòu)和性能的改變,與反式構(gòu)象HTAM2+··2ClO4-·H20相比,順式構(gòu)象TAM+··Cl-擁有一維高疏水通道。另外由于構(gòu)象的改變,二者展現(xiàn)出不同的磷光性能和磁化率值。
[Abstract]:In this paper, the progress of aryl methyl radical functional materials and the application of protonation in organic molecules are reviewed. In our previous research work, we synthesized a stable luminescent neutral radical substrates obip and obip-CHO. On this basis, we further developed the study of functional free radical materials. Firstly, two stable diarylmethyl monradical 5 and diarylmethyl triradical 7 were designed and synthesized by a simple one-pot method. The two free radicals exhibit different properties due to their different electronic structure and stacking state. After acidizing in HC1O4 solution, 5 can be easily converted to 7. 5%. Compared with 5, 7 has higher quantum yield and higher near infrared absorption, which is due to the unique proton sharing hydrogen bond in 7. In addition, the phosphorescence, color and magnetic properties between 5 and 7 can be converted to each other under the stimulation of acid-base gas, and different EPR signals are given accordingly. Therefore, the proton sharing hydrogen bond can be used as a switch between 5 and 7: when protonated, the switch "on" 7 is stable, and the EPR exhibits a seven-fold signal peak with fluorescence properties, and when the switch "off" 7 is deprotonated, the switch "off" 7 turns into a single signal peak. The weak 7. 7 luminescence can be used as a phosphorescence sensing device for ammonia due to its ability to respond to this kind of stimulation of acid and basic gas. This work provides a new synthesis method for the study of new multifunctional materials which can change color, luminescence and magnetism reversible by external stimulation, and provides inspiration for the fabrication of new sensing devices. Secondly, on the basis of the previous chapter, we continue to cultivate a single crystal in hydrochloric acid system, which has an interesting three-ring [6.2.0.0] configuration formed by the interaction of multiple hydrogen bonds. In addition, based on the crystallographic evidence of single crystals, we report for the first time an undissociated HC1 hydrate single crystal and the unconventional cis-linear conformation of its aqueous molecular dimer. It is also proved that the unique phenomenon is caused by the ring geometry effect of the three-ring configuration. The importance of this work lies in the discovery of undissociated HC1 hydrate single crystals at room temperature and the formation of cis-linear conformation water molecular dimers without cavity binding. Our work provides assistance for exploring new configurations of HC1-H20 system at room temperature. Finally, based on the three new triarylmethyl carbon cationic radicals reported previously in the laboratory, it is found that the three triarylmethyl carbon cationic radical salts are isomers and exhibit different magnetic susceptibility values at 300K. In this chapter, a triarylmethyl carbon cationic radical (labeled TAM Cl-O) is synthesized by a simple one-pot method. Interestingly, when it is protonated, "cis" TAM Cl- is transformed into "trans" triarylmethyl carbon cationic radical (labeled HTAM2 _ 2ClO _ 4-H _ 2O). The obvious conformation change is caused by the intramolecular hydrogen bond formed by an exocyclic carbonyl oxygen atom and protonated pyridine nitrogen atom. At the same time, the change of conformation also leads to the change of crystal structure and properties. Compared with the trans-conformation HTAM2 _ 2ClO _ 4-H _ 20, the cis-conformation TAM _ (Cl-) has one dimensional high hydrophobic channel. In addition, due to the change of conformation, they exhibit different phosphorescence properties and magnetic susceptibility values.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TB34

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相關(guān)期刊論文 前1條

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