發(fā)布時(shí)間：2018-03-20 03:04

  本文選題：雙光子吸收　切入點(diǎn)：二聚效應(yīng)　出處：《山東師范大學(xué)》2017年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：具有強(qiáng)雙光子吸收性質(zhì)的有機(jī)分子材料,在諸多領(lǐng)域具有較大的應(yīng)用潛能,例如3維光信息存儲(chǔ),光動(dòng)力療法和雙光子熒光顯微鏡(TPEM)等。尤其TPEM在活細(xì)胞組織中的應(yīng)用,更是獲得了廣泛的關(guān)注。因此,探索有機(jī)雙光子吸收材料的潛能與應(yīng)用,成為了科研工作者研究的熱潮。但是,在實(shí)驗(yàn)材料、器材、費(fèi)用等因素的限制下,在實(shí)驗(yàn)上探尋材料性能的速度與效率并不盡如人意。近年來(lái),通過(guò)量子化學(xué)計(jì)算理論研究雙光子吸收材料結(jié)構(gòu)與性能的關(guān)系,成為了諸多科研者的工作重點(diǎn)。理論研究可以指導(dǎo)實(shí)驗(yàn)分子的合成,從而大大節(jié)省了科研的時(shí)間與費(fèi)用。目前,一系列具有π共軛中心、電子給體(D)和受體(A)的對(duì)稱或不對(duì)稱的電荷轉(zhuǎn)移分子(如D-π-D,D-π-A,D-A-D等)在理論和實(shí)驗(yàn)上被廣泛研究。各種分子內(nèi)結(jié)構(gòu)因素(如分子平面性,給體和受體的強(qiáng)度,π共軛中心的電子特性等)和分子間相互作用(如聚集效應(yīng)和溶劑效應(yīng))對(duì)雙光子吸收性質(zhì)的影響有了充分地研究。因此,根據(jù)已有的分子結(jié)構(gòu)與性質(zhì)關(guān)系,理論設(shè)計(jì)性能優(yōu)良的雙光子吸收材料成為了可能。本文在雜化密度泛函水平上,理論研究了一系列由四苯基乙烯基團(tuán)構(gòu)建的有機(jī)分子體系,并討論了體系的結(jié)構(gòu)與性質(zhì)的關(guān)系。主要工作可分為以下二個(gè)部分:第一部分研究了一類(lèi)四苯基乙烯衍生物雙光子吸收性質(zhì)的二聚效應(yīng)和同分異構(gòu)效應(yīng);第二部分是基于四苯基乙烯衍生物,理論設(shè)計(jì)了一系列有機(jī)雙光子吸收分子結(jié)構(gòu),并計(jì)算了設(shè)計(jì)分子的雙光子吸收性質(zhì)。一、四苯基乙烯衍生物雙光子吸收性質(zhì)的二集效應(yīng)和同分異構(gòu)效應(yīng)計(jì)算了一類(lèi)新型四苯基乙烯衍生物ENPOMe分子及其同分異構(gòu)體的雙光子吸收性質(zhì)�？紤]了4種分子單體結(jié)構(gòu),統(tǒng)計(jì)了分子內(nèi)各苯環(huán)平面間的二面角,計(jì)算了各單體結(jié)構(gòu)的雙光子吸收截面。計(jì)算結(jié)果顯示,分子異構(gòu)對(duì)雙光子吸收性質(zhì)有重要影響,分子局部的平面性能夠增強(qiáng)分子的雙光子吸收強(qiáng)度。為了探索聚集效應(yīng),設(shè)計(jì)了12種共價(jià)鍵相連接的二聚體結(jié)構(gòu),并計(jì)算了它們的雙光子吸收性質(zhì)。研究發(fā)現(xiàn),分枝的線性排列能夠有效增強(qiáng)材料的雙光子吸收性質(zhì)。由于分枝與主干之間夾角相似的結(jié)構(gòu)具有類(lèi)似的分子內(nèi)共軛通道和電荷轉(zhuǎn)移能力,所以分子的雙光子吸收性質(zhì)也類(lèi)似。此外,分子局部的平面性和整體的線性可能是實(shí)驗(yàn)上觀測(cè)到的聚集誘導(dǎo)雙光子吸收增強(qiáng)的原因。二、基于四苯基乙烯衍生物雙光子吸收材料的分子設(shè)計(jì)在實(shí)驗(yàn)分子的基礎(chǔ)上,綜合利用已有的雙光子吸收分子結(jié)構(gòu)與性質(zhì)之間的關(guān)系,理論設(shè)計(jì)了一系列有利于增強(qiáng)雙光子吸收截面的分子結(jié)構(gòu)。通過(guò)改變分子中電子給體基團(tuán),增強(qiáng)給體的強(qiáng)度,設(shè)計(jì)了2種分子結(jié)構(gòu),相應(yīng)的雙光子吸收強(qiáng)度均比實(shí)驗(yàn)分子有所增強(qiáng)。同時(shí),還發(fā)現(xiàn),當(dāng)改變咔唑基與分子主體的連接方式時(shí),可以顯著提高雙光子吸收強(qiáng)度。通過(guò)參考已有的實(shí)驗(yàn)結(jié)果,設(shè)計(jì)了不同共軛橋連接的3種二聚體結(jié)構(gòu),結(jié)果顯示,采用乙烯和乙炔共軛橋連接的二聚體結(jié)構(gòu)與實(shí)驗(yàn)分子的二聚體結(jié)構(gòu)相比,在長(zhǎng)波范圍內(nèi),雙光子吸收有較大增強(qiáng)。因此,計(jì)算結(jié)果證實(shí)了我們的設(shè)計(jì)思路。理論設(shè)計(jì)的分子不僅具有較強(qiáng)的雙光子吸收,而且,由于分子均含有螺旋槳結(jié)構(gòu)的四苯基乙烯基團(tuán),所以同時(shí)具有聚集誘導(dǎo)發(fā)光特性,可以成為優(yōu)良的雙光子熒光探針?lè)肿印?br/>[Abstract]:With the organic molecular material with strong two-photon absorption properties, has great potential in many fields, such as 3 dimensional optical information storage, photodynamic therapy and two-photon fluorescence microscopy (TPEM). Especially TPEM in living tissues, it is widely concerned. Therefore, to explore the potential and application organic two photon absorption materials, has become a scientific research boom. However, in the experimental equipment, materials, costs and other factors limit, in the experiment to explore the speed and efficiency of material performance is not satisfactory. In recent years, the relationship through quantum chemical calculation theory of two-photon absorption material structure and performance, become many researchers focus on theoretical research. Synthetic molecules can guide the experiment, which saves the time and cost of scientific research. At present, a series of conjugated center electron donor (D) and Receptor (A) charge symmetric or asymmetric transfer molecules (such as D- -D D- -A PI, PI, D-A-D) in theory and experiment have been widely studied. The various factors in the molecular structure (such as molecular plane, donor and acceptor strength, conjugated center of electronic properties etc.) and intermolecular phase the interaction (such as aggregation effect and solvent effect) has been fully research on two-photon absorption properties. Therefore, according to the relationship between the molecular structure and properties, the theory of the design of excellent properties of two-photon absorption materials as possible. Based on the hybrid density functional theory research level, a series of four phenyl ethylene organic molecular systems group construction, and discusses the relationship between the structure and properties of the system. The main work can be divided into the following two parts: the first part is to study a class of four phenyl ethylene derivatives of two photon absorption properties of two poly effect and isomeric effect The second part is; four phenyl ethylene derivatives based on the theory, design a series of molecular structure of organic two-photon absorption, two-photon absorption properties and molecular design calculation. A two-photon, four phenyl ethylene derivatives of two-photon absorption properties of two in effect and the isomeric effect on a new class of four phenyl ethylene derivatives ENPOMe molecules and their isomers. Considering the absorption properties of 4 kinds of molecular monomer structure, the statistics of the dihedral angle between the benzene ring plane molecular two-photon, each monomer structure to calculate the absorption cross section is calculated. The results show that the molecular heterogeneity has an important effect on the two-photon absorption properties of planar molecules to local enhanced two photon absorption intensity. In order to explore the molecular aggregation effect, design two dimeric structure 12 covalently connected, their two-photon absorption properties were calculated. The results show that points Branch of the linear array can effectively enhance the two-photon absorption properties of materials. The structures are similar to the angle between the branch and the trunk has a similar intramolecular conjugated charge transfer and channel capacity, so the two-photon absorption properties of molecules are similar. In addition, the local molecular planarity and overall linear may be experimentally observed aggregation two photon induced absorption enhancement. Two, four phenyl ethylene derivatives of two photon absorption materials based on the molecular design of molecules based on the comprehensive utilization of the two-photon absorption molecular structure and properties of the theory, design a series is conducive to enhancing the two-photon absorption cross section by changing the molecular structure of electronic. The donor groups in the molecule, to enhance the strength, design 2 kinds of molecular structure, the corresponding two-photon absorption intensity than the experimental molecular improved. At the same time, also Found that when the connection mode change of carbazole and molecular entities, can significantly improve the two-photon absorption intensity. The experimental results with reference to the existing design, different conjugated bridge connecting 3 two dimer structure, results showed that the ethylene and acetylene conjugated bridge connecting two dimeric structure and experimental molecular poly two body structure than in the long wavelength range, two-photon absorption has greatly enhanced. Therefore, the calculated results proved that our design ideas. The molecular theory has not only design and better two-photon absorption, because, four phenyl vinyl group containing molecular structure of the propeller, so at the same time with aggregation induced emission, can become double photon fluorescent probe molecule excellent.

【學(xué)位授予單位】：山東師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O625.12

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 武香蓮;趙珂;賈海洪;王富青;;以二乙烯硫/砜基為中心的新型電荷轉(zhuǎn)移分子雙光子吸收特性[J];物理學(xué)報(bào);2015年23期

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本文編號(hào)：1637208