个人信息Personal Information
教授
博士生导师
硕士生导师
性别:男
毕业院校:吉林大学
学位:博士
所在单位:化工学院
学科:有机化学. 应用化学. 物理化学
办公地点:西部校区E座208房间
联系方式:0411-84986236
电子邮箱:zhaojzh@dlut.edu.cn
Covalently Bonded Perylene-DiiodoBodipy Dyads for Thiol-Activatable Triplet-Triplet Annihilation Upconversion
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论文类型:期刊论文
发表时间:2017-10-19
发表刊物:JOURNAL OF PHYSICAL CHEMISTRY C
收录刊物:Scopus、SCIE
卷号:121
期号:41
页面范围:22665-22679
ISSN号:1932-7447
摘要:To achieve activatable triplettriplet annihilation (TTA) upconversion, we linked a diiodoBodipy triplet photosensitizing unit and perylene triplet energy acceptor/annihilation/emitter using a disulfide bond (dyad BP-1), which can be selectively cleaved by thiols. For comparison, a reference dyad featuring a shorter and more chemically robust 1,2,3-triazole linker between the two components was also prepared (dyad BP-2). The photophysical properties of these compounds have been studied using steady-state and time-resolved transient spectroscopies; forward singlet energy transfer and backward triplet energy transfer (ping-pong energy transfer) were observed. For BP-1, the rate for forward intramolecular Forster resonance energy transfer from perylene to diiodoBodipy is k(FRET) = 1.9 x 10(8) s(-1), while the backward triplettriplet energy-transfer (TTET) process from diiodoBodipy to perylene was slightly slower, with k(TTET) = 3.7 x 10(7) s(-1). For BP-2, faster energy-transfer kinetics were determined (k(FRET) = 3.1 x 10(8) s(-1) and k(TTET) = 8.4 x 10(7) s(-1), respectively). Interestingly, we found the FRET rate constant is more critically dependent on the length of the linker than the corresponding TTET process, which may have important implications for the design of supramolecular TTA architectures. Lastly, upon cleavage of the disulfide bond in BP-1, intramolecular FRET was effectively shut down, and instead intermolecular TTET was observed, allowing for thiol-activatable TTA upconversion with an improvement in upconversion quantum yield from 0.03% to 0.5% in the presence of thiols.