Exciton Polariton-Enhanced Photodimerization of Functionalized Tetracene

Exciton Polariton-Enhanced Photodimerization of Functionalized Tetracene
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功能化并四苯的激子极化增强光二聚化

DOI:
10.1021/acs.jpcc.1c06881
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发表时间:
2021
期刊:
The Journal of Physical Chemistry C
影响因子:
--
通讯作者:
Ostroverkhova, Oksana
Ostroverkhova, Oksana
中科院分区:
--
文献类型:
--
作者:
Puro, Richard;Van Schenck, Jonathan D.;Center, Reid;Holland, Emma K.;Anthony, John E.;Ostroverkhova, Oksana

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我们探讨了功能化并四苯(TIPS-Tc)薄膜的光降解机制,以及它们如何受到平面微腔中强激子-光子耦合的影响。我们表明,暴露于空气中的TIPS-Tc膜的降解主要通过氧介导的途径进行,分配到内过氧化物(EPO)的形成,而在微腔中的降解通过氧独立的光二聚化进行。发现好氧和厌氧衰变机制的速率相差两个数量级以上。EPO的形成和光二聚化在有利于相关三重态对(TT)状态形成(单线态裂变的前体)及其周围环境的分子中进行得更有效。对于光二聚反应,炔二聚体被报道为光产物之一,并介绍了它的光学性质。TIPS-Tc与谐振微腔的强耦合使光二聚量子产率提高了4.2倍,增强相对于腔失谐是稳健的。
We explore the photodegradation mechanisms in functionalized tetracene (TIPS-Tc) films and how they are influenced by strong exciton–photon coupling in planar microcavities. We demonstrate that degradation of TIPS-Tc films exposed to air proceeds mainly through an oxygen-mediated pathway, assigned to endoperoxide (EPO) formation, whereas degradation in microcavities proceeds through oxygen-independent photodimerization. The aerobic and anaerobic decay mechanisms were found to differ in rate by more than two orders of magnitude. Both the EPO formation and photodimerization proceeded more efficiently in molecules in configurations favorable for the correlated triplet pair (TT) state formation (precursor to the singlet fission) and their immediate surroundings. For the photodimerization, an alkyne dimer is reported as one of the photoproducts, and its optical properties are presented. Strong coupling of TIPS-Tc to resonant microcavities enhanced the photodimerization quantum yield by a factor of 4.2, with the enhancement robust with respect to cavity detuning.
使用可见光的可溶性并四苯衍生物的光二聚化
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