共晶提升纯有机材料室温磷光余辉性能

doi:10.6023/cjoc202401023

有机化学 ›› 2024, Vol. 44 ›› Issue (8): 2588-2594.DOI: 10.6023/cjoc202401023 上一篇下一篇

研究论文

共晶提升纯有机材料室温磷光余辉性能

崔怡静^a^,^b, 朱天文^a^,^b, 张强^a^,^b, 袁望章^a^,^b^,^*()

a 上海交通大学化学化工学院变革性分子前沿科学中心上海市电气绝缘与热老化重点实验室上海电化学能源器件工程技术研究中心上海 200240
b 中国科学院青海盐湖研究所盐湖资源绿色高值利用重点实验室西宁 810008

收稿日期:2024-03-23 修回日期:2024-04-24 发布日期:2024-05-10
基金资助:
国家自然科学基金(52073172); 国家自然科学基金(U22A20250)

Cocrystallization Boosted Performance of Room Temperature Phosphorescence Afterglows from Pure Organics

Yijing Cui^a^,^b, Tianwen Zhu^a^,^b, Qiang Zhang^a^,^b, WangZhang Yuan^a^,^b()

a Shanghai Engineering Research Center for Electrochemical Energy Devices, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240
b Key Laboratory of Green and High-End Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008

Received:2024-03-23 Revised:2024-04-24 Published:2024-05-10
Contact: *E-mail: wzhyuan@sjtu.edu.cn
Supported by:
National Natural Science Foundation of China(52073172); National Natural Science Foundation of China(U22A20250)

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摘要/Abstract

纯有机超长寿命室温磷光(p-RTP)材料因其独特的光物理性质, 低成本, 结构可设计性及其在生物影像、疾病诊疗、传感与防伪加密等领域的应用前景引起了广泛关注. 然而, 要实现兼具高效且颜色可调的p-RTP余辉发射, 仍颇具挑战. 受簇聚诱导发光(CTE)机理启发, 选用三聚氰胺(MA)和环酰脲化合物海因(HA)及二氢尿嘧啶(DHU)作为电子给体和受体, 采用共晶策略制备了1∶1计量组成的共晶. 较MA、HA及DHU单组分晶体而言, 共晶展现出更好的p-RTP颜色可调性及更长寿命, 这是共晶中广泛存在C=O、孤对电子、多重氢键、适当电荷转移及多重簇发光中心等协同作用的结果, 并进一步展示了这些共晶材料在高端防伪保密领域的应用.

关键词: 超长寿命室温磷光, 余辉, 共晶, 簇聚诱导发光

Pure organic materials with persistent room-temperature phosphorescent (p-RTP) have attracted extensive attention due to their unique photophysical properties, low cost, design flexibility, and promising applications in such areas as biomedical imaging, disease diagnosis and treatment, sensing, and anti-counterfeiting encryption. Achieving efficient, long-lived, and tunable p-RTP afterglows, however, remains a significant challenge. Herein, inspired by the clustering- triggered emission (CTE) mechanism, utilizing the cocrystallization strategy, cocrystals with stoichiometric ratio of 1∶1 were prepared by employing melamine (MA) and cyclic acylureas of hydantoin (HA) and dihydrouracil (DHU) as electron donor and acceptors, respectively. Compared to the single-component crystals of MA, HA, and DHU, the cocrystals exhibited better color-tunability and longer lifetimes for p-RTP emissions, which are attributable to the synergistic effects of the widespread presence of C=O groups, lone pair electrons, multiple hydrogen bonds, appropriate charge transfer, and multiple emissive clusters. Furthermore, advanced anti-counterfeiting and encryption applications of these cocrystalss were demonstrated.

Key words: persistent room temperature phosphorescence, afterglows, cocrystallization, clustering-triggered emission

引用此文

崔怡静, 朱天文, 张强, 袁望章. 共晶提升纯有机材料室温磷光余辉性能[J]. 有机化学, 2024, 44(8): 2588-2594.

Yijing Cui, Tianwen Zhu, Qiang Zhang, WangZhang Yuan. Cocrystallization Boosted Performance of Room Temperature Phosphorescence Afterglows from Pure Organics[J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2588-2594.

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图/表 6

图1. MA、HA及DHU结构式及其共结晶系统的设计理念

Figure 1. Structures of MA, HA and DHU, and the cocrystallization design concept of the system

图2. HA和MA-HA (a)在285、312和365 nm紫外灯照射前后的发光照片和(b)不同λexs下的延迟(td=1 ms)光谱、(c) HA和(d) MA-HA磷光衰减曲线(<τp>为拟合的最长寿命值)以及(e)不同λexs下MA-HA晶体磷光发射的CIE坐标

Figure 2. (a) Photographs taken under 285, 312, and 365 nm UV lights or after ceasing the irradiations and (b) delayed (td=1 ms) emission spectra with different λexs of HA and MA-HA, RTP decay curves of (c) HA and (d) MA-HA (<τp> is the fitted maximum lifetime), and (e) CIE coordinate diagram of the p-RTP emission of MA-HA cocrystals with different λexs

图3. DHU和MA-DHU (a)在285、312和365 nm紫外灯辐照下及关闭辐照后的发光照片和(b)不同λexs下的延迟(td=1 ms)光谱、(c) DHU和(d) MA-DHU的磷光衰减曲线(<τp>为拟合的最长寿命值)以及(e)不同λexs下MA-DHU共晶p-RTP的CIE坐标

Figure 3. (a) Photographs taken under 285, 312, and 365 nm UV lights or after ceasing the irradiations and (b) delayed (td=1 ms) emission spectra with different λexs of DHU and MA-DHU, RTP decay curves of (c) DHU and (d) MA-DHU (<τp> is the fitted maximum lifetime), and (e) CIE coordinate diagram of the p-RTP emission of MA-DHU cocrystals with different λexs

图4. MA-HA共晶的结构、分子间相互作用及分子堆积

Figure 4. Structures, intermolecular interactions, and molecular packing of MA-HA cocrystals

图5. (a)单分子激发态表面电势能图及(b)单分子HOMO、LUMO能级电子密度分布

Figure 5. (a) Electric potential distributions of the excited states of monomers and (b) electron density distributions of HOMO and LUMO levels for momomers

图6. MA-HA共晶在多模式高端防伪加密领域的应用展示

Figure 6. Demonstration of the multi-mode anticounterfeiting and encryption applications of MA-HA cocrystals

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共晶提升纯有机材料室温磷光余辉性能

Cocrystallization Boosted Performance of Room Temperature Phosphorescence Afterglows from Pure Organics

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