<br>掺杂晶体的高效红色/近红外磷光,Angewandte Chemie International Edition

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掺杂晶体的高效红色/近红外磷光
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2024-08-23 , DOI: 10.1002/anie.202412967
Zihao Zhao ₁ , Tianwen Zhu ₂ , Anze Li ₂ , Qiang Zhang ₂ , Wang Zhang Yuan ₃

Affiliation

具有低毒性和易于合成的有机红/近红外（NIR）室温磷光（RTP）材料备受追捧，特别是在生物技术和加密领域的应用。然而，由于有机物的自旋轨道耦合较弱以及能隙定律带来的快速非辐射衰减，实现高效的红光/近红外 RTP 发射器一直具有挑战性。在这里，我们通过将邻苯二甲酰亚胺 (PAI) 的硫代衍生物（MTPAI 和 DTPAI）掺杂到 PAI 晶体中，展示了高效的红色/近红外 RTP，量子产率 (Φp) 高达 32.96%。红移光致发光（PL）源于外部重原子效应和以富电子硫原子为中心的发射簇的形成的结合。此外，掺杂剂提高了激子产生效率，促进能量从较小的 PAI 单元转移到较大的聚集体，从而显着增加 Φp。事实证明，该策略具有普遍性，为获取具有可调光物理特性的长波长 RTP 提供了可能性。掺杂晶体在光波导和加密纸/墨水中具有广阔的应用前景。这项研究提供了一种获得长波长 RTP 材料的实用方法，并为主客体系统的控制机制提供了宝贵的见解。

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Highly Efficient Red/Near-Infrared Phosphorescence from Doped Crystals

Organic red/near-infrared (NIR) room temperature phosphorescence (RTP) materials with low toxicity and facile synthesis are highly sought after, particularly for applications in biotechnology and encryption. However, achieving efficient red/NIR RTP emitters has been challenging due to the weak spin–orbit coupling of organics and the rapid nonradiative decay imposed by the energy gap law. Here we demonstrate highly efficient red/ NIR RTP with boosted quantum yields (Φp) of up to 32.96% through doping the thionated derivatives of phthalimide (PAI) (MTPAI and DTPAI) into PAI crystals. The red-shifted photoluminescence (PL) stems from a combination of the external heavy atom effect and the formation of emissive clusters centered around electron-rich sulfur atoms. Furthermore, the dopants enhance exciton generation efficiency and facilitate energy transfer from smaller PAI units to larger aggregates, leading to dramatically increased Φp. This strategy proves universal, opening possibilities for acquiring long-wavelength RTP with tunable photophysical properties. The doped crystals exhibit promising applications in optical waveguides and encryption paper/ink. This research provides a practical approach to obtaining long-wavelength RTP materials and offers valuable insights into the mechanisms governing host-guest systems.

更新日期：2024-08-23

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