光谱学与光谱分析, 2018, 38 (3): 715, 网络出版: 2018-04-09   

9, 10-二杂环取代蒽衍生物制备与三线态-三线态湮灭上转换性能研究

Synthesis of 9,10-Diheterocyclicanthracenes and Performance Correlations in Triplet-Triplet Annihilation Upconversion
作者单位
1 苏州科技大学化学生物与材料工程学院, 环境功能材料省重点实验室, 江苏 苏州 215009
2 山东大学晶体材料国家重点实验室, 山东 济南 250100
摘要
弱光上转换是基于三线态-三线态湮灭机制将低能量(长波长)的光转换为高能量(短波长)光的一种现象, 是通过光敏剂与发光剂之间能量转移实现的。 针对当前上转换体系中的光敏剂研究备受关注, 而对于同等重要作用的发光剂的研究甚少的现状, 利用Suzuki偶联反应制备了两个新的杂环取代蒽衍生物: 9, 10-二(3-呋喃)蒽(DFA)和9, 10-二(3-噻吩)蒽(DTA)并通过结构表征; 以9, 10-二杂环取代蒽为发光剂、 四苯基卟啉钯衍生物(PdTPPMe和PdTPPCOOH)为三线态光敏剂, 研究所构成的光敏剂/发光剂双组分体系中, 三线态-三线态能量转移效率(kQ)、 发光剂的延迟荧光寿命(τDF)及发光剂荧光量子产率(Φf)等因素对上转换效率(ΦUC)的影响。 结果表明, 高效三线态-三线态能量效率(ΦTTT)、 快速延迟荧光寿命和大荧光量子产率将有利于提高上转换效率。 进一步研究发现, 含氧发光剂(DFA)与含羧基的光敏剂(PdTPPCOOH)之间可借助氢键发生有效耦合, 有利于光敏剂与发光剂之间的三线态能量转移, 导致弱光上转换效率显著提高。 在半导体激光器(532 nm, 70 mW·cm-2)激发下获得强的绿-转-蓝上转换效率最大可达10.11%。 所获得的绿-转-蓝上转换荧光可使Pt/WO3复合半导体受激; 产生氧自由基并可促使香豆素转化为7-羟基香豆素。
Abstract
Low-power photon upconversion (UC) can convert low-energy photons to high-energy photons based on triplet-triplet annihilation (TTA) mechanism, which invloves a bimolecular system containing a sensitizer and an emitter (acceptor) . Firstly, the sensitizer harvests the excitation energy toward its triplet excited state with intersystem crossing (ISC), then the triplet energy of the sensitizer is transferred to the acceptor (i.e., triplet-triplet energy transfer, TTT). Lastly, two excited triplet acceptors would annihilate (i.e., triplet-triplet annihilation, TTA) while one of them irradiates the high-energy light (upconversion) from the excited state to the ground state. Since the processes mentioned above, including ISC, TTT and TTA, are transition-allowed, the TTA-UC can be achieved at ultra-low excitation power that is less than the terrestrial solar radiation (ca. 100 mW·cm-3), which shows wide spread practical applications such as in solar cells. Compared to the development of triplet sensitizers, little attention has been paid to the development of triplet acceptors. Here, two new compounds: 9,10-Di(3-furan)anthracence (DFA) and 9, 10-di(3-thiophene)anthracence (DTA) were synthesized as the triplet acceptor (emitter) that can doped with palladium(Ⅱ) tetraphenylporphyrin derivatives (PdTPPMe or PdTPPCOOH) to obtain the triplet sensitizer/acceptor bimolecular system. Under the low-power excitation of the diode laser (532 nm, 70 mW·cm-2), these bimolecular systems could emit strong green-to-blue upconversion with the efficiencies (ΦUC) in the order of DFA/PdTPPCOOH (10.11%)>DTA/PdTPPCOOH (7.20%)>DFA/PdTPPMe (6.31%)>DFA/PdTPPMe (5.45%). The obtained results have shown that large triplet-triplet quenching constant (kQ), high prompt fluorescence quantum (Φf) and fast delayed fluorescence (τDF) are responsible for effective upconversion efficiency (ΦUC). Moreover, it was found that oxygen-containing 9, 10-di(3-furan)anthracence (DFA) and PdTPPCOOH within the mixed alcohol media can effectively interact each other based on the hydrogen bond (H-bond) and resulting larger triplet-triplet quenching constant (kQ), which have contribution to enhancement the upconversion efficiency. With the help of Pt/WO3 photo-catalyst, the conversion from coumarin to 7-hydroxycoumarin was successfully achieved under the irradiation of our green-to-blue upconversion produced with bimolecular DFA/PdTPPCOOH in alcohol media.

陈佳, 叶常青, 朱赛江, 王筱梅, 陶绪堂. 9, 10-二杂环取代蒽衍生物制备与三线态-三线态湮灭上转换性能研究[J]. 光谱学与光谱分析, 2018, 38(3): 715. CHEN Jia, YE Chang-qing, ZHU Sai-jiang, WANG Xiao-mei, TAO Xu-tang. Synthesis of 9,10-Diheterocyclicanthracenes and Performance Correlations in Triplet-Triplet Annihilation Upconversion[J]. Spectroscopy and Spectral Analysis, 2018, 38(3): 715.

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