本文選題：氯原子 + 溴原子��； 參考：《華中科技大學(xué)》2014年博士論文

【摘要】：本論文探索出將氯原子引入到共軛聚合物主鏈的直接聚合方法,并將主鏈含有氯原子的共軛聚合物成功應(yīng)用到聚合物發(fā)光二極管中；同時合成出側(cè)鏈含有溴原子的共軛聚合物,探究了側(cè)鏈溴原子對共軛聚合物光學(xué)性能、電化學(xué)性能的影響,并將其作為給體材料應(yīng)用到有機/聚合物太陽能電池中。具體內(nèi)容和主要結(jié)論概述如下： 設(shè)計合成了2,3-雙(3-正辛烷氧基苯基)-5,8-二溴-6,7-二氯喹喔啉,利用該分子中氯原子和溴原子在Stille反應(yīng)中反應(yīng)活性的差異,將其與2,5-雙三甲基錫噻吩聚合,首次成功制備出主鏈含氯原子的、結(jié)構(gòu)規(guī)整的給體-受體交替共聚物(PC1QT)。同時合成出其氟代(PFQT)、未取代(PQT)的結(jié)構(gòu)相似的聚合物,以便系統(tǒng)研究氯原子對共軛聚合物性能的影響。盡管氯原子的電負(fù)性低于氟原子的電負(fù)性,但PC1QT比PFQT具有更深的LUMO能級。通過量子計算發(fā)現(xiàn),與氟原子不同的是,氯原子扭曲了聚合物主鏈,使LUMO能級局域在受體單元中。這可能是PC1QT具有更低的LUMO能級的原因。而使用聯(lián)噻吩雙錫鹽作為給體單元合成的含氯聚合物PC1Q2T,與PC1QT相比,具有相似的LUMO能級和較高的HOMO能級。說明含氯共軛聚合物的HOMO和LUMO能級可以獨立調(diào)控。同時因為氯原子的位阻效應(yīng),這些含氯共軛聚合物的吸收光譜明顯的藍(lán)移,Stokes位移增大,自吸收減小。 以2,3-雙(3-正辛烷氧基苯基)-5,8-二溴-6,7-二氯喹喔啉為受體單元,調(diào)節(jié)給體單元中噻吩個數(shù),合成出三種紅光聚合物材料PC1Q2HT、PC1Q3T和PC1Q4T。將PC1Q2HT、 PC1Q3T和PC1Q4T作為客體材料,選用高效綠光材料F8BT為主體材料,制備聚合物發(fā)光二極管器件。以PC1Q3T為客體材料制備出了發(fā)光峰位于678nm,色坐標(biāo)為(0.66,0.34),亮度接近2000cd m-2,外量子效率超過1%的深紅光聚合物發(fā)光二極管。以PC1Q4T為客體材料制備出了發(fā)光峰位于692nm,色坐標(biāo)為(0.67,0.32),亮度接近1500cd m-2的深紅光聚合物發(fā)光二極管；發(fā)光峰位于708nm,色坐標(biāo)為(0.69,0.31),亮度超過400cd m-2,外量子效率超過0.6%的近紅外聚合物發(fā)光二極管。 設(shè)計合成出4,7-二溴-5,6-二氯苯并[1,2,5]噻二唑,并以其為受體單元合成出共軛聚合物。由于該分子內(nèi)氯原子和溴原子的反應(yīng)活性在Stille反應(yīng)中差異較小,無法作為單體直接用于聚合；但可以通過Suzuki聚合得到主鏈含氯原子的共軛聚合物。將氯原子引入到苯并噻二唑單元上,會使聚合物材料的LUMO能級升高。分析量子計算結(jié)果,推斷造成氯原子在喹喔啉體系和苯并噻二唑體系中對能級調(diào)控作用差異的原因可能是喹喔啉和苯并噻二唑中吡嗪環(huán)和噻二唑環(huán)的電子能力和位阻存在差異。以4,7-二(5-溴-2-噻吩基)-5,6-二氯苯并[1,2,5]噻二唑為受體單元,以2,7-雙頻哪醇硼酸酯-芴為給體單元合成的聚合物PFC1DTBT作為客體材料以3%的濃度摻雜到主體綠光材料F8BT中,制備出器件結(jié)構(gòu)為ITO/PEDOT:PSS(30nm)/F8BT:聚合物(100nm)/Ca (20nm)/Al(100nm)的聚合發(fā)光二極管器件,電致發(fā)光峰位于632nm處,色坐標(biāo)為(0.60,0.40),亮度最大可以達(dá)到15580cd m-2,電流效率為1.2cd A-1,最大外量子效率為1.1%。 將溴原子引入到給體材料的側(cè)鏈,通過調(diào)節(jié)含溴單元的比例,合成出一系列給體材料。發(fā)現(xiàn)在溶液中,聚合物的摩爾吸光系數(shù)隨著含溴比例的變化有先減小后增大的趨勢,熒光光譜峰值隨溴含量的增加而逐漸紅移；薄膜狀態(tài)時,隨著含溴比例的增加,吸收光譜中的肩峰越發(fā)明顯,但聚合物的熒光光譜基本相同。這是因為溴原子被極化后與材料間的偶極-偶極相互作用弱于聚合物鏈段間的偶極-偶極相互作用。溶液中聚合物鏈段間相互作用較弱,枝接在側(cè)鏈的溴原子被極化后對材料的影響得以顯現(xiàn)；但薄膜狀態(tài)時,聚合物鏈段間相互作用占主導(dǎo)地位。同時溴原子引入的分子間弱相互作用,促進(jìn)了材料的堆積,使吸收光譜中肩峰的強度隨溴含量的提高而增強。
[Abstract]:This paper will explore the chlorine atom by direct polymerization of conjugated polymer backbone, and conjugated polymers containing chlorine atom backbone successfully applied to polymer light emitting diode; at the same time the synthesis of conjugated polymers with side chain containing bromine atom, explores the side chain of bromine atoms on the optical properties of conjugated polymers, affect the electrochemical performance, and as to the material applied to organic / polymer solar cells. The specific contents and main conclusions are as follows:
The design and synthesis of 2,3- (3- is octyloxy phenyl) -5,8- -6,7- two dibromo dichloro quinoxaline, using chlorine atom or bromine atoms in the molecular differences in reactivity in the Stille reaction, the 2,5- dual three methyl tin thiophene polymerization, have been prepared for the first time the backbone of the chlorine atoms, regular structure to acceptor alternating copolymer (PC1QT). At the same time the synthesis of fluorinated (PFQT), unsubstituted (PQT) polymers with similar structure, in order to study the chlorine atom of conjugated polymer system performance. Although the chlorine atom electronegativity below the electronegativity of fluorine, but PC1QT is deeper than LUMO level PFQT. Through quantum computing, unlike fluorine atom, chlorine atom has distorted the polymer backbone, the LUMO level in the local receptor unit. This may be the reason why LUMO PC1QT has a lower level. And the use of bithiophene double tin salt as donor cell synthesis The chlorine containing polymer PC1Q2T, compared with PC1QT, HOMO has the similar LUMO level and higher level. The results showed that HOMO and LUMO levels of chlorine containing conjugated polymers can independently control. At the same time because of the steric effect of chlorine atoms, the chlorine absorption spectra of conjugated polymer obviously blue shift and Stokes displacement increases, self absorption decreases.
2,3- (double 3- octane oxygen phenyl) -5,8- dibromo dichloro quinoxaline -6,7- two receptor unit, adjusted to the unit in a number of thiophene, synthesis of three kinds of red polymer PC1Q2HT, PC1Q3T and PC1Q4T. PC1Q2HT, PC1Q3T and PC1Q4T as the guest material, the efficient use of green materials F8BT as main material, preparation polymer light emitting diode device. Using PC1Q3T as the guest material prepared by the emission peak at 678nm, and color coordinates of (0.66,0.34) 2000cd m-2, close to the brightness of light emitting diode, deep red polymer external quantum efficiency of more than 1%. With PC1Q4T as the guest material prepared by the emission peak at 692nm, and color coordinates of (0.67,0.32) deep red, light emitting diode brightness close to 1500cd polymer m-2; emission peak at 708nm, and color coordinates of (0.69,0.31) 400cd, brightness of more than m-2, the external quantum efficiency of more than 0.6% of the near infrared polymer light emitting diode.
The design and synthesis of 4,7- -5,6- and [1,2,5] dibromo two chlorobenzene Thiadiazolen two triazole, and its receptor unit synthesis of conjugated polymer. The reactivity of the molecules in the chlorine and bromine atoms in the Stille reaction between small, can not be used as monomer for polymerization; it can be conjugated polymer backbone containing a chlorine atom by Suzuki polymerization. The chlorine atoms into the dibenzothiophene was two units, will make the LUMO level of polymer materials increased. The results of quantum, caused by chlorine atoms inferred regulation of the level in the system of quinoxaline and dibenzothiophene two triazole system as the reason for the difference may be electronic ability of quinoxaline and dibenzothiophene in two were: in the two ring and thiophene thiazole ring and steric differences. In two 4,7- (5- bromo -2- thienyl) -5,6- two and [1,2,5] two were for chlorobenzene thiazide receptor unit to unit was synthesized by 2,7- dual band which alcohol boric acid ester - fluorene The polymer PFC1DTBT as the object of materials with doping concentration of 3% to the main green materials in F8BT, prepared by the device structures of ITO/PEDOT:PSS (30nm) /F8BT: polymer (100nm) /Ca (20nm) /Al (100nm) polymer light emitting diodes, light emitting peaks are located at 632nm, and color coordinates of (0.60,0.40), maximum brightness can reach 15580cd m-2, the current efficiency was 1.2cd A-1 1.1%., the maximum external quantum efficiency
The bromine atom is introduced into the material of the side chain, by adjusting the proportion of bromine containing unit, synthesized a series of donor materials found in the polymer solution, the molar absorption coefficient is decreased first and then increased with the change of bromine containing ratio, increase the peak of fluorescence spectrum with bromine content gradually shift film; state, with the increase of the proportion of bromine, absorption peak of the more obvious, but the fluorescence spectra of the polymers are basically the same. This is because the bromine atom is polarized with the material of the dipole dipole interaction between polymer chains is weaker than the dipole dipole interaction. The weaker interaction between polymer chains between the grafting solution, after being polarized effect on the material of bromine atoms of side chains; but the film state, polymer chain interactions dominate. At the same time the introduction of molecular bromine atoms between weak interactions It is used to promote the accumulation of the material, so that the intensity of the acromion in the absorption spectrum is enhanced with the increase of the bromine content.

【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TQ317;TM914.4

【共引文獻(xiàn)】

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