蒽衍生物取代基团与三线态-三线态湮灭上转换性能关系研究  

The Influence of Substituents in Anthracene Derivatives on the Performance of Triplet-Triplet Annihilation Upconversion

作　　者：梁作芹[1] 晏旭 宋冬冬 张晓波 张家璇 叶常青[1] 陈硕然 王筱梅[1] LIANG Zuo-qin;YAN Xu;SONG Dong-dong;ZHANG Xiao-bo;ZHANG Jia-xuan;YE Chang-qing;CHEN Shuo-ran;WANG Xiao-mei(School of Materials Science and Engineering,Suzhou University of Science and Technology,Suzhou 215009,China)

机构地区：[1]苏州科技大学材料科学与工程学院,江苏苏州215009

出　　处：《光谱学与光谱分析》2022年第3期802-807,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(51803147);江苏省环境功能材料重点实验室开放课题(SJHG1803);江苏省大学生创新创业训练计划项目(202010332083E)资助。

摘　　要：三线态-三线态湮灭(TTA)上转换是一种以低功率非相干光泵浦实现大的反斯托克位移的光谱转换技术,具有激发和发射波长可调的特点,在提高太阳能利用率方面具有重要应用价值。经过十几年的发展,敏化剂分子的研究取得了很大进步,而发光剂分子的研究相对落后。以敏化剂多吡啶钌(Ⅱ)配合物[Ru(bpy)_(2)Phen]^(2+)和发光剂2-位取代的蒽衍生物(DTACl和DTACN)作为研究对象,复配得到两个弱光上转换体系。通过敏化剂与发光剂的发射和上转换光谱性质,系统研究了蒽2-位取代基团对发光效率、三线态-三线态能量传输(TTET)、TTA等能量传递过程的影响。研究发现DTACl具有比DTACN高的荧光量子产率、大的三线态猝灭常数和高的TTA效率,这些结果最终使得[Ru(bpy)_(2)Phen]^(2+)/DTACl的上转换效率高于[Ru(bpy)_(2)Phen]^(2+)/DTACN。除此之外,利用敏化剂、发光剂的发射光谱,结合密度泛函理论计算,进一步从轨道能级的角度,研究了敏化剂、发光剂三线态能级差与TTET效率之间的关系,以及发光剂三线态与单线态能级差与TTA效率之间的关系。研究结果表明:降低蒽2-位取代基团的吸电子能力,能有效提高发光剂的三线态能级水平,从而减小发光剂与敏化剂的三线态能级差,增大发光剂的三线态与单线态能级差,提高发光剂与敏化剂之间的TTET效率、发光剂的TTA效率,进而提高体系的TTA上转换效率。该工作为开发新型、高效的发光剂分子提供了一种简单、可行的设计思路。Triplet-triplet annihilation(TTA)upconversion is a spectral conversion technique with large anti-stoke shift under the incoherent low-power photoexcitation.And the excitation and emission wavelengths are adjustable.Therefore,TTA upconversion has an important application value in improving solar energy utilisation.Tremendous advances have been made on the sensitizers,but the research on the emitters is relatively backward.In this paper,2-substituted anthracene derivatives(DTACl and DTACN)were used as the emitter doped with Ru(Ⅱ)polypyridine complex[Ru(bpy)_(2)Phen]^(2+)(as the sensitizer)to set up the TTA upconversion models.The effects of anthracene 2-substituents on the luminescence efficiency,triplet-triplet energy transfer(TTET),TTA have systematically studied through the emission and upconversion spectra of the sensitizer the emitter.It is found that DTACl has higher fluorescence quantum yield,larger triplet quenching constant and higher TTA efficiency than DTACN.These results make the upconversion efficiency of[Ru(bpy)_(2)phen]^(2+)/DTACl higher than that of[Ru(bpy)_(2)phen]^(2+)/DTACN.Additionally,from the aspect of orbital energy level,the relationship between the triplet energy difference of the sensitizer and the emitter and the TTET efficiency,as well as the relationship between the singlet/triplet energy difference of the emitter and the TTA efficiency,were studied based on the emission spectra and the density functional theory calculation.The research results show that reducing the ability of the 2-substituted group to withdraw electrons can effectively improve the triplet energy level,which is conducive to the TTET efficiency due to the decrease of the triplet energy difference between the emitter and the sensitizer.At the same time,it is good for the TTA efficiency due to the increase of the emitter’s singlet/triplet energy difference.The triplet energy level has an important influence on the TTA upconversion efficiency.This work provides a simple and feasible method for designing new and effici

关 键 词：三线态-三线态湮灭 上转换 蒽 取代基团 构效关系 

分 类 号：O657.3[理学—分析化学]