个人信息Personal Information
教授
博士生导师
硕士生导师
主要任职:Director, State Key laboratory of Fine Chemicals
其他任职:精细化工国家重点实验室主任、国务院学科评议组成员
性别:男
毕业院校:大连理工大学
学位:博士
所在单位:化工学院
学科:应用化学. 精细化工. 化学生物学
办公地点:大连理工大学精细化工国家重点实验室
西部校区化工实验楼F-202#
http://peng-group.dlut.edu.cn/
联系方式:大连理工大学精细化工国家重点实验室 西部校区化工实验楼F-202 辽宁省大连市高新区凌工路2号,大连116024 Tel: 0411-84986306; Fax: 0411-84986292;课题组网址:http://peng-group.dlut.edu.cn/
电子邮箱:pengxj@dlut.edu.cn
Unexpected Nucleophilic Substitution Reaction of BODIPY: Preparation of the BODIPY-TEMPO Triad Showing Radical-Enhanced Intersystem Crossing
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论文类型:期刊论文
发表时间:2018-02-21
发表刊物:EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
收录刊物:SCIE
卷号:2018
期号:7
页面范围:885-895
ISSN号:1434-193X
关键字:Functional organic materials; Heterocycles; Luminescence; Upconversion; Nucleophilic substitution
摘要:We have discovered a new and unexpected substitution reaction of BODIPY. Through single-crystal XRD analysis, DFT calculations, and other complimentary spectroscopic methods, we have confirmed that the molecular structural assignment of the previously reported nucleophilic substitution of the halogenated carbon atom at the meso position of BODIPY was inaccurate. Indeed, in these substitution reactions, the amino attaches to the methyl group at the 3- or 5-position and not on the meso-carbon of the BODIPY core. As a result of this unexpected substitution reaction, we prepared a BODIPY dimer, attached to the stable radical TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxyl). We confirmed the efficient formation of the triplet state (phi = 59%, (T) = 2.8 mu s) of this BODIPY-TEMPO triad through the radical-enhanced intersystem crossing mechanism by using nanosecond time-resolved transient absorption spectroscopy. Through time-resolved EPR spectroscopy, the doublet (spin angular momentum quantum number S = 1/2) and quartet (S = 3/2) states of the triad were observed. Moreover, we observed a strong intramolecular ground-state interaction between the BODIPY chromophores in the triad, which shows new spectral features different to those of H- or J-aggregates and the exciton coupling effect. These TEMPO-labeled compounds were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion (quantum yield phi(UC) = 4.7%).