【作者】 李鹏飞；

【导师】 徐海军；

【作者基本信息】 南京林业大学 ， 化学工艺， 2022， 硕士

【摘要】 BODIPY类有机荧光染料因其具有良好的光学性质以及出色的可修饰性,通过引入多种不同功能的基团对BODIPY中心骨架结构进行共轭修饰以调整其光物理性质,使得其被广泛应用于荧光成像、光学材料、荧光探针、有机太阳能电池、光动力疗法等多个领域。本文选择以BODIPY为核心,利用Knoevenagel缩合、Sonogashira偶联反应在其不同活性位点引入具有不同电子能力的基团对其进行共轭修饰,成功设计并合成了五个不同系列共轭修饰BODIPY衍生物,通过核磁共振谱、高分辨质谱、MADLI-TOF质谱、X单晶衍射对它们的结构进行了表征,并使用紫外-可见吸收光谱仪、稳态/瞬态荧光光谱仪、电化学工作站等仪器对他们的光物理性质以及电化学性质进行了研究。主要研究内容如下:（1）通过两步Knoevenagel缩合反应合成了两种星型非富勒烯太阳能电池受体1a和1b。对其在作为有机太阳能电池器件中的光学性质、能级、形态和光伏性能方面进行了研究。研究发现,P:1a显示出较宽的吸收范围、改进的电荷迁移率、有效的激子解离和更好的形貌,这些优势使得基于P:1a的有机太阳能电池光电转化效率（PCE）达到13.41%、开路电压(V_OC)为1.02 V、短路电流(J_SC)为19.92 m A/cm²、填充因子（FF）为0.66,明显高于基于P:1b的器件。这项工作将为设计基于BODIPY衍生物的新型π共轭非富勒烯太阳能电池受体提供实验依据。（2）通过“氨解-Knoevenagel缩合”串联反应,一锅合成五种不同的单边和双边共轭修饰的BODIPY衍生物,而且一步得到3、5位不对称共轭修饰的BODIPY衍生物。光物理性质研究发现,引入吸电子基团的化合物2a、2b、2f和2k的量子产率均大于0.59,荧光寿命均长于7 ns。3、5位不对称产物2c、2g和2j不仅荧光寿命均长于2.2 ns,荧光量子产率均大于0.19,而且最大斯托克斯位移可达到69 nm,均发射出近红外荧光。该项研究将为高效合成光物理性质优异的近红外BODIPY衍生物提供新的思路。（3）通过两步Knoevenagel缩合反应合成了具有大斯托克斯位移的1、3、5、7共轭修饰BODIPY类衍生物3a-d。随着1、7位引入基团给电子能力的不断增强,化合物3a-d的分子内电荷转移效应越来越强,化合物3b和3c的斯托克斯位移分别可达到110 nm和92 nm。并且,3b-d表现出较强的溶剂依赖性,其中3c与3d在不同溶剂中最大吸收分别可达到53 nm和92 nm的红移。不同比例混合溶剂中,化合物3a-d均可以形成J-聚集体,且3c的最大吸收波长可红移至778 nm。结合其大的斯托克斯位移,3c极具潜力成为近红外二区荧光染料被应用于荧光成像、光动力治疗（PDT）等领域。（4）以不同meso-BODIPY衍生物为母体,通过Knoevenagel反应合成3,5位双边香豆素基共轭修饰的BODIPY类衍生物5a-d。化合物5b-d最大吸收波长红移显著,分别位于830 nm、770 nm以及761 nm。并且5b和5c在非极性溶剂中最大吸收波长可分别红移至890 nm和902 nm。不同比例混合溶剂中,5b-d的最大吸收波长也可分别红移至860 nm、861 nm以及802 nm,使得化合物5b-d具有成为近红外二区荧光染料的潜力。（5）通过Knoevenagel反应以及Sonogashira偶联在BODIPY母体结构2、3、5、6位进行共轭修饰合成了化合物7a和7b。化合物7a和7b最大吸收波长红移显著,分别位于770 nm和782 nm,发射波长分别位于818 nm和819 nm。不同比例混合溶剂中,化合物7a最大吸收波长出现141 nm的红移,可达到919 nm。其具有潜力成为近红外二区荧光染料被应用于荧光成像、PDT等领域。更多还原

【Abstract】 BODIPY organic fluorescent dyes have good optical properties and excellent modifiability,by introducing a variety of different functional groups to conjugate the BODIPY central skeleton structure to modify its photophysical properties,making it widely used in fluorescent imaging,optical materials,fluorescent probes,organic solar cells,photodynamic therapy and other fields.In this paper,five different series of conjugated BODIPY derivatives were successfully designed and synthesized by using Knoevenagel condensation and Sonogashira coupling to introduce groups with different electron capabilities at their different active sites to conjugate and modify BODIPY,and their structures were characterized by nuclear magnetic resonance（NMR）spectroscopy,high-resolution mass spectrometry（H-RMS）,MADLI-TOF mass spectrometry,and X-ray single crystal diffraction.Their photophysical properties and electrochemistry properties were studied using ultraviolet-visible absorption spectrometer,steady-state/transient fluorescence spectrometer,electrochemical workstation and other instruments.The main research contents are as follows:（1）Two star-type non-fullerene solar cell receptors 1a and 1b were synthesized by a two-step Knoevenagel condensation reaction.The optical properties,energy levels,morphology and photovoltaic properties of organic solar cell devices are studied.It is found that P:1a shows a wider absorption range,improved charge mobility,efficient exciton dissociation,and better morphology,which allows P:1a-based organic solar cells to achieve 13.41%photoelectric conversion efficiency（PCE）,open circuit voltage(V_OC)is 1.02 V,short circuit current(J_SC)is19.92 m A/cm²,and filling factor（FF）is 0.66,which is significantly higher than that of P:1b-based devices.This work will provide experimental basis for the design of novelπconjugated non fullerene solar cell receptors based on BODIPY derivatives.（2）Through the"aminolysis-Knoevenagel condensation"tandem reaction,five completely different unilateral and bilateral conjugated modified BODIPY derivatives were synthesized in one pot,and the 3,5-position asymmetrically conjugated BODIPY derivatives were obtained in one step.The photophysical properties study found that the quantum yields of compounds 2a,2b,2f and 2k introduced with electron withdrawing groups were all not lower than 0.59,and the fluorescence lifetimes were all longer than 7 ns.The 3,5-position asymmetric products 2c,2g and 2j not only have fluorescence lifetimes longer than 2.2 ns,fluorescence quantum yields are not lower than 0.19,but also the maximum Stokes shift can reach 69 nm,and all emit near-infrared（NIR）fluorescence.This study will provide new ideas for the efficient synthesis of NIR BODIPY derivatives with excellent photophysical properties.（3）1,3,5,7 conjugated modified BODIPY derivatives 3a-d with large Stokes shift were synthesized by two-step Knoevenagel condensation reaction.With the continuous enhancement of the electron donating ability of the introduced groups at positions 1 and 7,the intramolecular charge transfer effect of compounds 3a-d becomes stronger and stronger,and the Stokes shifts of compounds 3b and 3c can reach 110 nm and 92 nm respectively.Moreover,3b-d showed strong solvent dependence.The maximum absorption of 3c and 3d in different solvents can reach a red shift of 53 nm and 92 nm,respectively.In different proportions of mixed solvents,compounds 3a-d can form J-aggregates.Among them,the maximum absorption wavelength of3c can be red shifted to 778 nm.Combined with its large Stokes shift,3c has great potential to become a NIR-II fluorescent dye,which is used in fluorescence imaging,photodynamic therapy（PDT）and other fields.（4）Using different meso-BODIPY derivatives as precursors,3,5 bilateral coumarin based conjugated BODIPY derivatives 5a-d were synthesized by Knoevenagel reaction.The maximum absorption wavelength of compound 5b-d red shifted significantly to 830 nm,770nm and 761 nm,respectively.Moreover,the maximum absorption wavelengths of 5b and 5c in nonpolar solvents can be red shifted to 890 nm and 902 nm,respectively.In different proportions of mixed solvents,the absorption wavelengths of 5b-d can also be red shifted to860 nm,861 nm and 802 nm respectively,making compound 5b-d have the potential to become a NIR-II fluorescent dye.（5）Compounds 7a and 7b were synthesized by Knoevenagel reaction and Sonogashira coupling at positions 2,3,5 and 6 of BODIPY parent structure.The maximum absorption wavelengths of compounds 7a and 7b have a significant red shift,which are located at 770 nm and 782 nm respectively,and the emission wavelengths are located at 818 nm and 819 nm,respectively.In different proportions of mixed solvents,the maximum absorption wavelength of compound 7a shows a red shift of 141 nm,which can reach 919 nm.It has the potential to become a NIR-II fluorescent dye,which is used in fluorescence imaging,PDT and other fields.更多还原