【摘要】：本論文致力于發(fā)展新型噻吩硫硼摻雜的有機(jī)π共軛體系,主要分為兩個(gè)部分:第一部分雙噻吩稠合1,4-硼硫雜苯的合成及性質(zhì)研究;第二部分是雙苯并噻吩稠合1,4-硼硫雜苯的性質(zhì)研究。我們成功地合成了上述兩種含硼多環(huán)芳香烴的母體,并對(duì)其光電物理特性進(jìn)行了深入地研究,探究分子結(jié)構(gòu)與材料性能之間的關(guān)系。主要內(nèi)容如下:在第一部分工作中,我們?cè)O(shè)計(jì)合成了噻吩稠合1,4-硫硼雜苯化合物Ⅰ-1和Ⅰ-2,起初我們采用錫硼交換反應(yīng)的方法合成了目標(biāo)化合物,后期為避免使用含錫的有毒試劑,我們對(duì)合成方法進(jìn)行了改進(jìn),利用米基硼酸二甲酯作為親電試劑,兩步即可得到目標(biāo)化合物。隨后我們培養(yǎng)并得到了噻吩稠和1,4-硼硫雜苯的同分異構(gòu)體的單晶,通過(guò)對(duì)它的單晶進(jìn)行結(jié)構(gòu)解析,以及結(jié)合理論計(jì)算,我們認(rèn)為噻吩稠合1,4-硼硫雜苯具有弱的芳香性。我們還對(duì)其光電物理性質(zhì)進(jìn)行了詳細(xì)的研究。研究發(fā)現(xiàn),利用堿拔氫/親電體捕捉以及Stille偶聯(lián)反應(yīng)可以對(duì)Ⅰ-1和Ⅰ-2的2,4-位置進(jìn)行衍生化。我們也同時(shí)對(duì)部分衍生物進(jìn)行了光電物理性質(zhì)的研究。研究發(fā)現(xiàn),Ⅰ-1和Ⅰ-2在引入取代基之后吸收和發(fā)射波長(zhǎng)均會(huì)顯示一定程度的紅移。另外,對(duì)于Ⅰ-1和Ⅰ-2作為氟離子傳感器也進(jìn)行了初步地研究,我們發(fā)現(xiàn)加入F-后,Ⅰ-1和Ⅰ-2的吸收和發(fā)射受到明顯的抑制,此性質(zhì)表明Ⅰ-1和Ⅰ-2中的硼原子仍然具有一定的Lewis酸性。在第二部分工作中,基于第一部分工作的基礎(chǔ),我們?cè)O(shè)計(jì)并合成苯并噻吩稠合1,4-硫硼雜環(huán)化合物Ⅱ-1和Ⅱ-2,隨后利用同樣新的方法得到了目標(biāo)產(chǎn)物,我們也對(duì)Ⅱ-1和Ⅱ-2的單晶結(jié)構(gòu)進(jìn)行了詳細(xì)的研究,并且測(cè)試了Ⅱ-1和Ⅱ-2的紫外吸收、熒光發(fā)射、與F-絡(luò)合后的吸收發(fā)射以及循環(huán)伏安曲線。研究發(fā)現(xiàn),苯并噻吩稠和的1,4-硼硫雜苯的光電物理性質(zhì)與硼硫的相對(duì)位置有很大的關(guān)系。此外,此類化合物在空氣中非常穩(wěn)定,可以作為并五苯的類似物�？傊�,本論文圍繞噻吩稠和的含硼多環(huán)芳烴進(jìn)行了研究,設(shè)計(jì)并合成了兩個(gè)系列含硼的多環(huán)芳香烴,研究了其結(jié)構(gòu)與性質(zhì)的關(guān)系,為后續(xù)將此類多環(huán)共軛芳香烴應(yīng)用到有機(jī)光電材料中去奠定了一定的基礎(chǔ)。
[Abstract]:The present paper is devoted to the development of a new type of organosulfur-boron-doped organic carbon-benzene system, which is mainly divided into two parts: the synthesis and properties of the fused 1,4-boron-thiazene in the first part, and the properties of the 1,4-boron-thiazene fused by the second part. In this paper, we successfully synthesized the parent of the two kinds of boron-containing polycyclic aromatic hydrocarbons, and carried out in-depth study on the photoelectric physical properties of the two kinds of boron-containing polycyclic aromatic hydrocarbons, and explored the relationship between the molecular structure and the material property. The main contents are as follows: In the first part of the work, we designed the compound I-1 and I-2 of the 1,4-thiobo-benzo-benzo-azobenzene compounds I-1 and I-2, at the beginning, we synthesized the target compound by the method of the tin-boron exchange reaction, and the later period is to avoid the use of the tin-containing toxic reagent. The synthesis method is improved, and the target compound can be obtained in two steps by using the methyl-based boric acid dimethyl ester as the electrophilic reagent. The single crystals of the isomers of 1,4-boron-thiazobenzene are then cultured and obtained. By structural analysis of its single crystal and the theoretical calculation, we consider that the 1,4-boron-thiazene has a weak aromaticity. We have also studied the photoelectrical properties in detail. It is found that the 2,4-position of I-1 and I-2 can be derivatised by means of alkaline extraction of hydrogen/ electrophile capture and the Stille coupling reaction. We also study the photoelectrical properties of some of the derivatives at the same time. It was found that the absorption and emission wavelength of I-1 and I-2 after the introduction of the substituents showed a certain degree of redshift. In addition, I-1 and I-2 were also studied as a fluoride ion sensor. We found that the absorption and emission of I-1 and I-2 were significantly inhibited after F-1 and I-2, which indicated that the boron atoms in I-1 and I-2 still have a certain Lewis acidity. in that work of the second part, based on the basis of the work of the first part, we design and synthesize the benzo-1,4-thiobo-heterocyclic compound II-1 and II-2, and then using the same new method to obtain the target product, We also studied the single crystal structure of 鈪，

本文編號(hào)：2453956