Theoretical and Experimental Investigations on the Aggregation‐Enhanced Emission from Dark State: Vibronic Coupling Effect,Advanced Electronic Materials

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Theoretical and Experimental Investigations on the Aggregation‐Enhanced Emission from Dark State: Vibronic Coupling Effect
Advanced Electronic Materials ( IF 5.3 ) Pub Date : 2020-06-09 , DOI: 10.1002/aelm.202000255
Ping‐An Yin _{1,

2} , Qing Wan ₁ , Yingli Niu ₃ , Qian Peng ₂ , Zhiming Wang ₁ , Yuxuan Li ₁ , Anjun Qin ₁ , Zhigang Shuai ₄ , Ben Zhong Tang _{1,

5}

Affiliation

Aggregation‐induced/‐enhanced emission (AIE/AEE) has aroused broad interest. The mechanism behind is understood as the aggregation restriction of the nonradiative decay from electronically excited state to the ground state, either through interconversion or through conical intersection, leaving the dipole‐allowed radiative decay channel relatively intact. Here, a report on an AEE phenomenon for 5,10‐diphenylphenazine (DPhPZ) compound is presented, for which the experiment shows to be AEE active but the lowest excited state has been long known to be “dark state,” namely with zero transition dipole with the ground state according to Kasha’s rule. The computational studies demonstrate that the optical emission stems from the “dark state” with emission intensity borrowed from higher‐lying “bright state” through Herzberg–Teller vibronic coupling, and the resultant spectra are in good agreement with the experiment in terms of both line shape and peak position. The vibronic‐coupling‐induced radiative decay and the restricted nonradiative decay synergistically bring about highly efficient luminescence of DPhPZ in the solid phase. The findings open a new avenue for the development of solid‐emissive luminophores.

中文翻译：

暗态聚集增强发射的理论和实验研究：振动耦合效应

聚集诱发/增强的排放（AIE / AEE）引起了广泛的关注。背后的机理被理解为通过互变或通过圆锥形相交从电子激发态到基态的非辐射衰减的聚集限制，而使偶极子辐射衰减通道相对完整。在这里，提供了一份有关5,10-二苯基吩嗪（DPhPZ）化合物的AEE现象的报告，该实验表明该化合物具有AEE活性，但长期以来人们一直知道最低激发态是“暗态”，即零跃迁根据Kasha的规则，偶极子处于基态。计算研究表明，光发射源自“暗态”，其发射强度通过Herzberg-Teller振动耦合从较高的“亮态”中借用，谱线和峰位均与实验结果吻合良好。振动耦合引起的辐射衰变和受限制的非辐射衰变协同产生了固相中DPhPZ的高效发光。这些发现为固态发光体的发展开辟了一条新途径。

更新日期：2020-07-13

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