本文關(guān)鍵詞：鄰位含氟偶氮苯光控開(kāi)關(guān)分子內(nèi)電荷轉(zhuǎn)移的理論研究　出處：《遼寧大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 鄰位四基含氟偶氮苯 電子-空穴相干性 離域 拉電子性基團(tuán) 順?lè)串悩?gòu)化

【摘要】：置身信息時(shí)代的浪潮中，海量的信息存儲(chǔ)使人們對(duì)光信息存儲(chǔ)材料的需求十分迫切。偶氮苯—新型光致變色化合物中的一種，以其卓越的光學(xué)特性—光致變色順?lè)串悩?gòu)性，在生物材料、光信息材料等眾多領(lǐng)域炙手可熱，成為光信息存儲(chǔ)材料中的寵兒。 然而偶氮苯自身卻存在兩大不容忽視的缺點(diǎn)。首先是利用紫外光，必須通過(guò)*激發(fā)來(lái)誘導(dǎo)反→順異構(gòu)化，但卻潛在地影響和破壞了周圍的環(huán)境；其次是不完全可逆的順→反光異構(gòu)化，這種異構(gòu)化需要可見(jiàn)光輻射來(lái)誘導(dǎo)，但此時(shí)順、反異構(gòu)物的n*吸收帶常被忽略，因此在分子翻轉(zhuǎn)后不能表現(xiàn)出E（反）異構(gòu)物豐富的光穩(wěn)定性。我們可以通過(guò)調(diào)整偶氮苯分子的化學(xué)結(jié)構(gòu)，消除上述弊端，改善其物理化學(xué)性質(zhì)。 在本論文中，我們將利用2,6-二氟苯胺合成鄰位四基含氟偶氮苯，通過(guò)在鄰位含氟偶氮苯的對(duì)位引入氨酰基這類給電子性的基團(tuán)（EDGS）和酯基這類拉電子性的基團(tuán)（EWGS），來(lái)調(diào)節(jié)光譜特征，擴(kuò)大吸收量和n*吸收帶的間隔。分子1以N-acyl基團(tuán)作為電子給體（donor）,o-fluoroazobenzenes基團(tuán)作為電子受體（acceptor）；對(duì)于分子2，o-fluoroazobenzenes成為電子給體，電子受體是拉電子性的ester基團(tuán)。本文中，我們主要采用量子化學(xué)方法進(jìn)行理論研究。運(yùn)用密度泛函理論（Density Functional Theory，DFT）中的B3LYP函數(shù)和DZVP基組對(duì)分子1和分子2的順?lè)串悩?gòu)物進(jìn)行幾何結(jié)構(gòu)優(yōu)化，并對(duì)其基態(tài)、激發(fā)態(tài)性質(zhì)進(jìn)行理論研究和計(jì)算，同時(shí)列出分子相對(duì)最高占據(jù)分子軌道（the highest occupied molecular orbital, HOMO）和最低未占據(jù)分子軌道（the lowest unoccupied molecular orbital, LUMO）以及相對(duì)應(yīng)的能量。分子1的反、順異構(gòu)物的主要峰值是403.18nm和329.84nm，分別是HOMO→LUMO和HOMO-1→LUMO軌道電子躍遷的結(jié)果；分子2的反、順異構(gòu)物的主要峰值為371.65nm和468.66nm，分別是兩軌道HOMO-1→LUMO和HOMO-4→LUMO。為了深入研究分子1和分子2的激發(fā)態(tài)性質(zhì)，，我們?cè)诒菊撐闹凶龀隽朔肿?和分子2的UV吸收光譜和圓二色光譜。對(duì)于分子內(nèi)電荷轉(zhuǎn)移情況，我們利用三維實(shí)空間分析方法，將分子1、分子2的電荷轉(zhuǎn)移過(guò)程可視化。躍遷密度（TD）揭示偶極矩躍遷轉(zhuǎn)變方向和強(qiáng)度，電荷差異密度（CDD）顯示了分子內(nèi)電荷躍遷的方向和結(jié)果,DOS揭示了原子態(tài)密度在HOMO和LUMO軌道上的分布情況。利用2維（2D）實(shí)空間分析方法來(lái)分析電子-空穴的相干性和電子離域，進(jìn)而比較三維實(shí)空間分析結(jié)果與二維實(shí)空間分析結(jié)果的一致性。
[Abstract]:In the tide of information age, mass information storage makes the demand of optical information storage material very urgent. Azobenzene is one of the new photochromic compounds. Because of its excellent optical properties, photochromic discoloration and anti-isomerism are popular in many fields, such as biomaterials, optical information materials and so on, and become the favorite of optical information storage materials. However, azobenzene itself has two shortcomings that can not be ignored. First, the use of ultraviolet light must be induced by excitation. 鈫扖is-isomerization, but potentially affecting and destroying the surrounding environment; followed by incomplete reversible cis-isomerization. 鈫扲eflective isomerization, which requires visible light radiation to induce the isomerization, but the N * absorption bands of the cis-trans isomers are often ignored. Therefore, the photostability of E- (inverse) isomers can not be shown after the molecular inversion. We can eliminate the above disadvantages by adjusting the chemical structure of azobenzene molecules and improve their physical and chemical properties. In this thesis, we will synthesize o-tetrafluoroazobenzene from 2-fluoro-6-difluoroaniline. The spectral characteristics were regulated by the introduction of electron-giving groups such as aminoyl groups (EDGSs) and electron-pulling groups such as ester groups (EWGSN) into the p-fluoroazobenzene containing o-fluoroazobenzene. The distance between the absorption band and the absorption band of n * is enlarged. Molecule 1 is composed of N-acyl group as the electron donor). The o-fluoroazobenzenes group was used as the electron acceptor. For the molecular 2- fluorofluoroazobenzenes as an electron donor, the electron acceptor is an electron-pulling ester group. We mainly use the quantum chemical method to study the theory and the density functional theory (Density Functional Theory). B3LYP function and DZVP basis set are used to optimize the geometric structure of the cis-trans isomers of molecule 1 and molecular 2, and the properties of ground state and excited state are studied and calculated theoretically. At the same time, the relative highest occupied molecular orbital of the highest occupied molecular orbital is listed. Homo) and the lowest unoccupied molecular orbital, the lowest unoccupied molecular orbital. Lumo) and the corresponding energy. The main peak values of cis-isomers of molecule 1 are 403.18 nm and 329.84 nm, respectively, which are HOMO. 鈫扡UMO and HOMO-1. 鈫扵he results of electron transition of LUMO orbitals; the main peaks of molecular 2 are 371.65 nm and 468.66 nm, respectively, which are two-orbital HOMO-1. 鈫扡UMO and HOMO-4. 鈫捍n order to study the excited state properties of molecule 1 and molecular 2, we have made UV absorption spectra and circular dichroism spectra of molecule 1 and molecular 2 in this thesis. Using three-dimensional real space analysis method, we visualize the charge transfer process of molecule 1 and molecule 2. The transition density (TD) reveals the transition direction and intensity of dipole moment transition. The charge difference density (CDD) shows the direction and result of intramolecular charge transition. DOS reveals the distribution of atomic density of states on HOMO and LUMO orbitals. The coherence and delocalization of electron holes are analyzed by using the real space analysis method. Then the consistency between the results of 3D real space analysis and two dimensional real space analysis is compared.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2014
【分類號(hào)】：TP333;O561

【共引文獻(xiàn)】

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