喹吖啶酮分子的合成与结构及光物理荧光机制  

Synthesis,Structure and Photophysical Fluorescence Mechanism of Quinacridone Molecules

作　　者：王甦昊 胡明霞 陈卉 赵彦英[1] Wang Suhao;Hu Mingxia;Chen Hui;Zhao Yanying(School of Chemistry and Chemical Engineering,Zhejiang Sci-Tech University,Hangzhou 310018,China)

机构地区：[1]浙江理工大学化学与化工学院,杭州310018

出　　处：《化学学报》2024年第9期925-931,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(No.22273086)资助.

摘　　要：喹吖啶酮(QA)为具有强共轭作用的平面型分子,在溶液中表现出强荧光发射.由于分子间强的π-π堆积作用,固体反而会荧光淬灭,致使在荧光染料、显示、传感和光电器件中的应用受到诸多限制.然而,当QA骨架引入特定空间取向的官能团可大大改善其光学活性并提高荧光发射效率,本工作通过连接三氟甲基苯基官能团(-PhCF3)合成了强固体荧光分子QA-CF3,并利用吸收和荧光光谱探讨了其光学性质与分子结构之间的关系.在二甲基亚砜溶液中,QA和QA-CF3均有强荧光,QA-CF3的紫外吸收和发射波长相较QA均发生了不同程度的蓝移,其中QA和QA-CF3的最大发射波长分别为547和536 nm,蓝移了11 nm.然而,与QA固体荧光淬灭不同,QA-CF3固体表现出强荧光发射,最大发射波长红移至631.4 nm.含时密度泛函理论(TD-DFT)计算表明QA-CF3中的-PhCF3取代基平面与QA几乎垂直,恰好限制了QA间的π-π堆积作用,从而促进了QA-CF3的辐射跃迁,致使荧光增强;同时,吸电子-PhCF3官能团增大了QA-CF3分子跃迁能,为紫外吸收和发射波长相较于QA蓝移的原因.Quinacridone(QA)possesses excellent color fastness and weather resistance,making it largely contribute to industrial coatings,pigments,and printing inks.Additionally,QA derivatives have been applied in the field of organic solar cells due to their strong absorption in the visible regions.The hyperconjugative planar structure of QA derivative molecules effectively facilitates efficient carrier transport in organic field-effect transistors(OFETs).Combined with their excellent optical,thermal,and electrochemical stability,QA derivatives hold potential as materials for organic light-emitting diodes(OLEDs).However,the planar QA,renowned for its intense fluorescence emission in solution due to strong conjugation effects,encounters fluorescence quenching in its solid state due to robustly intermolecularπ-πstacking interactions between molecules.This quenching significantly constrains its applications in fluorescent dyes,displays,sensors,and optoelectronic devices.To address this limitation,the introduction of trifluorobenzene functional groups(-PhCF3)with spatially extended orientation into the QA framework has been explored.The resulting compound,QA-CF3,was synthesized and its photophysical and photochemical properties were compared to QA using UV-Vis absorption and fluorescence spectroscopies.In solution,both QA and QA-CF3 exhibited strong fluorescence emission,with QA-CF3 displaying a blue shift in its UV absorption and emission wavelengths compared to QA.Specifically,the maximum emission wavelengths of QA and QA-CF3 are 547 and 536 nm in dimethyl sulfoxide,respectively,representing a blue shift of 11 nm.In contrast to the fluorescence quenching of solid QA,solid QA-CF3 exhibits intense fluorescent emission,with the maximum emission wavelength red-shifted to 631.4 nm.Time-dependent density functional theoretical(TD-DFT)calculations reveal that the-PhCF3 plane is nearly perpendicular to the QA plane,effectively mitigating the intermolecularπ-πstacking interactions.This spatial orientation facilitates irradiative t

关 键 词：喹吖啶酮 Π-Π堆积作用 荧光增强 紫外-可见吸收光谱 荧光光谱 

分 类 号：O641.1[理学—物理化学]