【作者】 王晓慧；

【导师】 冯星；

【作者基本信息】 广东工业大学 ， 材料工程（专业学位）， 2023， 硕士

【摘要】 作为煤化工的副产品,芘因其优异的蓝光性质、高量子产率和良好的电荷传输性质而备受瞩目。一方面,芘是一类强致癌的化工产品,对环境产生严重的危害,同时芘又是一种重要的化工原料,广泛的应用于化工、医药、有机光电等领域。芘有十个可以发生功能化取代的活性位点,按其反应活性由高到低分为三类:活性位点(1-,3-,6-和8-位)、K-区位点(4-,5-,9-和10-位)和平面节点位点(2-和7-位)。一般来说,不同位点取代的芘基衍生物展现出的物理、化学性质迥异。因此,采用合理的化学合成手段,制备各类新型芘基化工中间体,并构建出不同分子构型、具有不同功能的芘基功能材料,引起了工业界和学术界的极大兴趣。本论文以芘为原料,秉承“变废为宝”的分子设计理念,采用合理的化学合成手段,实现对芘的特定位点进行有序可控的修饰,制备新型的芘基中间体;进一步地,基于自主开发的芘基中间体,设计合成了系列芘基衍生物,并对其光物理性质进行了深入研究探讨。具体研究内容包括以下三部分:(1)新型芘基中间体的可控合成。以芘为原料,选用羟基作为定位基团,通过卤代反应,成功将卤素原子有序可控的取代在1-,3-,6-,8-位,制备了多种新型芘基中间体:2-羟基-1-溴芘(2a)、2-羟基-1,3-二溴芘(2b)、2-羟基-1,3,6-三溴芘(2c)、2-羟基-1,3,6,8-四溴芘(2d)、2,7-二羟基-1,3,6,8-四溴芘(2e)、2-羟基-1-氯芘(2f)和2-羟基-1,3-二氯芘(2g)。优化了合成方案,芘基中间体的产率高达80%,并系统研究了羟基对亲电反应的影响,及有序可控卤代的反应机理。(2)多位点取代的芘基蓝光材料的设计合成及光物理性质研究。以自主开发的芘基中间体2d和2e为原料,采用Suzuki-Miyaura偶联反应分别引入甲氧基苯和三氟甲基苯,设计合成了五个新型芘基衍生物3a-3e。通过紫外-可见吸收光谱、荧光光谱、X-射线衍射分析和理论计算对五个化合物的光物理性质进行了详尽的分析和表征:3a-3e在溶液中均表现出优异的深蓝光发射性质,由于羟基的存在具有一定的空间立体效应,导致多位点取代芘基发光分子的荧光发射峰变窄,而且通过调节-OH的数目、调控分子间的相互作用,产生了力致荧光增强的特性。结合理论计算和实验,系统研究了分子聚集-分子间相互作用对芘基发光材料聚集态光物理性质的影响。(3)新型芘并呋喃衍生物的制备及其双光子吸收性质研究。以自主开发的溴芘中间体2d为原料,通过Sonogashira偶联反应一步合成的方法,成功制备了四个具有芘并呋喃分子骨架的化合物5a-5d。通过紫外-可见吸收光谱、荧光光谱系统研究了这类大π共轭的芘并呋喃分子的发光行为,结合理论计算阐明了分子结构-分子堆积与发光性质之间的关系。四个化合物在溶液中表现出高效的绿色荧光发射,由于分子的大平面结构,在聚集状态下容易发生较强的π-π相互作用,导致聚集态的荧光红移。此外,这类分子表现出良好的双光子吸收特性,通过调控末端取代基团的种类,其双光子截面最大可以调节至533 GM,可作为优异的双光子荧光探针以应用于细胞成像。更多还原

【Abstract】 As a byproduct of coal chemical industry,pyrene has attracted much attention due to its excellent blue light properties,high quantum yield and good charge transport properties.On the one hand,pyrene is a kind of carcinogenic chemical products,causing serious harm to the environment.On the other hand,pyrene is also an important chemical raw material,widely used in chemical,medicine,organic photoelectric and other fields.Pyrene has ten functional substitution active sites,which can be divided into three categories in order of reactivity from high to low:common sites(1,3,6,8-sites),K-sites(4,5,9,10-sites),and node-plane sites(2,7-sites).Generally speaking,pyrene-based derivatives substituted by different sites show different physical and chemical properties.Therefore,it is of great interest to the industrial and academic circles to prepare all kinds of new pyrene chemical intermediates and to develop pyrene functional materials with different molecular configurations and functions via reasonable chemical synthesis methods.In this thesis,pyrene was selected as the parent material,adhering to the molecular design concept of"turning waste into treasure",choosing reasonable chemical synthesis routes to achieve the specific sites of pyrene orderly and controllable modified,prepare new pyrene intermediates.Furthermore,a series of pyrene derivatives were designed and synthesized based on independently developed pyrene intermediates,and their photophysical properties were carefully investigated.The specific research content includes the following three parts:(1)Controlled synthesis of novel pyrene intermediates.Choosing pyrene as the raw material,hydroxyl group was selected as the positioning group.Halogen atoms were successfully replaced in the 1-,3-,6-and 8-positions in an orderly and controllable manner through halogenation reaction,and a variety of novel pyrene intermediates were prepared:2-hydroxy-1-bromopyrene(2a),2-hydroxy-1,3-dibromopyrene(2b),2-hydroxy-1,3,6-tribromopyrene(2c),2-hydroxy-1,3,6,8-tetrabromopyrene(2d),2,7-dihydroxy-1,3,6,8-tetrabromopyrene(2e),2-hydroxy-monochloropyrene(2f),and 2-hydroxy-1,3-dichloropyrene(2g).The synthesis scheme was optimized,the yield of pyrene intermediate was up to 80%,and the effect of hydroxyl group on electrophilic reaction and the reaction mechanism of orderly controlled halogenation were systematically studied.(2)Design,synthesis and photophysical properties of multi-site substituted pyrene based blue emission materials.Five novel pyrene derivatives 3a-3e were designed and synthesized via pyrene-based intermediates 2d and 2e by Suzuki-Miyaura coupling reaction with the introduction of methoxy benzene and trifluoromethyl benzene,respectively.The photophysical properties of the five compounds were analyzed and characterized by UV-vis absorption spectrum,PL spectrum,X-ray diffraction analysis and theoretical calculation.3a-3e exhibited excellent photophysical properties of deep blue emission in solution.Due to the presence of hydroxyl,the emission peaks of these pyrene based luminescent molecules became more narrow,and the mechanical force-induced enhanced emission was caused by regulating the number of-OH and the interaction between molecules.Combining with theoretical calculation and experiment,the effect of molecular aggregation and intermolecular interaction on the photophysical properties of pyrene based luminescent materials was systematically studied.(3)Synthesis and two-photon absorption property study of novel pyrene-based derivatives.Four compounds 5a-5d with pyreno[2,1-b]furan skeleton were synthesized by Sonogashira coupling reaction with bromopyrene intermediate 2d as precursor.The luminescence behavior of pyreno[2,1-b]furan molecules with highπconjugated was studied by UV-vis absorption and PL spectra,and the relationship between molecular structure,packing mode and luminescence properties was elucidated by theoretical calculations.Four compounds exhibit efficient green emission in solution,and strongπ-πinteraction occurs easily in aggregated state due to the large planar structure of the molecules,leading to fluorescence redshift.In addition,these molecules behave good two-photon absorption characteristics,and the maximum two-photon cross section can be adjusted to 533 GM by adjusting the type of terminal substituent groups,which can be applyed in cell imaging.更多还原