Broadband Visible Light Harvesting BODIPY-Perylene Dyad and Triad:Synthesis,Photophysical Properties,and Photooxidation Applications  

具有较宽可见光捕获范围的二碘氟硼荧-花二联体和三联体:合成、光物理性质及其在光氧化方面的应用

作　　者：Yu Gong Lei Dong Qiang-Qiang Shen Meng Li Yi-Nuo Gu Wei-Guang Zhang Xin-Yu Xue Qing-Jin Xue San-E Zhu Yu-Mei Zhou 龚宇;董磊;申强强;李梦;谷一诺;张威光;徐欣雨;薛庆锦;朱三娥;周玉梅(合肥大学能源材料与化工学院,合肥230601;浙江太湖远大新材料股份有限公司,湖州313100)

机构地区：[1]School of Energy,Materials and Chemical Engineering,Hefei University,Hefei 230601,China [2]Zhejiang Taihu YuanDa New Material Corp.,Ltd.,Huzhou 313100,China

出　　处：《Chinese Journal of Chemical Physics》2024年第4期545-552,I0067-I0079,I0094,I0095,共23页化学物理学报（英文）

基　　金：supported by the Research Project for Outstanding Young People in Universities of Anhui Province(No.2023AH030099);the China Postdoctoral Science Foundation(No.2023M733378);the National Natural Science Foundation of China(No.21702042,No.22305059,No.22103010);the National University Students'Innovation and Entrepreneurship Training Program(No.202311059024);the Anhui Provincial Natural Science Foundation(No.2308085QB59);the Anhui Provincial Excellent Scientific Research and Innovation Team(No.2022AH010096).

摘　　要：In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.本文采用二碘氟硼荧作为能量供体,3,4,9,10-花四甲酸二酐作为能量受体,成功合成了两种新型化合物:二碘氟硼荧~花二联体和三联体,为进一步研究能量供体对分子光物理性质的影响,本文在二碘氟硼黄-花二联体中引入了一个二碘氟硼荧单元和一个3.4.9.10-花四甲酸二酐单元,而二碘氟硼荧-花三联体中引入了两个二.碘氟硼荧单元和一个3.4.9.10-花四甲酸二酐单元.得益于二碘氟硼荧和3,4,9,10-花四甲酸二酐之间的良好光谱互补性,这两种化合物在400~620 nm的波长范围内展示了较好的光捕获能力.稳态荧光光谱分析显示,在二碘氟嫻荧-花二联体和二碘氟硼荧菲三联体中当二碘氟硼荧单元被选择性激发时,能高效地将能量转移给3,4,9,10-花四甲酸二酐;相反,当3,4,9,10-花四甲酸二酐单元被选择性激发时,能观察到属于3,4,9,10-花四甲酸二酐的荧光发生明显猝灭.纳秒级瞬态吸收光谱分析表明,二碘氟硼荧-花二联体和二碘氟硼荧-北三联体均能有效地生成属于3,4,9,10-非四甲酸二酐部分的三重激发态.二碘氟硼荧-非二联体和二碘氟硼黄-非三联体的三重态寿命分别为103和89us,比二碘氟硼荧的三重态寿命长.光氧化实验进一步显示,二碘氟硼荧-二联体和二碘氟硼荧-花三联体都具有优异的光稳定性和光氧化能力,其中二碘氟硼荧-花三联体的光氧化能力高于二碘氟硼荧-花二联体,其光氧化速率常数为二碘氟硼荧-花二联体的1.3倍,单线态氧量子产率为二碘氟硼荧-花二联体的1.6倍。这些结果为设计新型光敏剂提供了重要的理论支持.

关 键 词：BODIPY PERYLENE Triplet excited states Nanosecond transient absorption PHOTOOXIDATION 

分 类 号：TQ422[化学工程]