{"title":"原子精确金纳米团簇的压力激活高效近红外发光。","authors":"Ya-Ni Yang,Qiu-Yang Wan,Meng-Jie Zhu,Hua-Yang Ru,Ji-Kun Yang,Qi Li,Meng Zhou,Gaosong Chen,Yuchen Wu,Lei Jiang,Shuang-Quan Zang","doi":"10.1021/jacs.5c09304","DOIUrl":null,"url":null,"abstract":"Achieving efficient near-infrared (NIR) luminescence in atomically precise gold nanoclusters is challenging due to the strong vibrational freedom of the gold core. Herein, we synthesized two gold nanoclusters, [Au11(PPh3)8Cl2]Cl (Au11-1) and Au11(PPh3)7Cl3 (Au11-2), with comparable initial NIR photoluminescence quantum yields (PLQY, 0.3% and 0.32%, respectively), and systematically investigated their NIR piezoluminescence behaviors based on the hydrostatic pressure effect. Under high pressure, Au11-1 exhibits a significant NIR piezoluminescence enhancement. When the pressure increases to 3.6 GPa, the NIR-PLQY of Au11-1 amplifies from the initial 0.3% to 75.6%, which is the highest PLQY reported for solid-state gold nanoclusters. However, Au11-2 exhibits only monotonic pressure-induced luminescence quenching under compression. In situ high-pressure angle-dispersive X-ray diffraction experiments and theoretical calculations confirm the existence of distinct anisotropic compressions in Au11-1 and Au11-2, which induce differential structural distortion of the gold core. The faster shrinkage along the a-axis exacerbates the structural distortion of the Au11-1 core, whereas the more rapid compression along the b-axis in Au11-2 suppresses the structural distortion of the gold core. High-pressure femtosecond transient absorption and Raman spectra synergistically demonstrate that pressure-driven directional structural distortion significantly suppresses nonradiative losses caused by low-frequency vibrations of the Au11-1 core along the a-axis, resulting in NIR piezoluminescence enhancement of Au11-1. Our study deeply reveals the intrinsic correlation between NIR-PLQY and metal core vibration relaxation at the atomic scale and provides a new approach to design and develop high-performance NIR luminescent materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":14.4000,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Pressure-Activated Efficient Near-Infrared Luminescence in Atomically Precise Gold Nanoclusters.\",\"authors\":\"Ya-Ni Yang,Qiu-Yang Wan,Meng-Jie Zhu,Hua-Yang Ru,Ji-Kun Yang,Qi Li,Meng Zhou,Gaosong Chen,Yuchen Wu,Lei Jiang,Shuang-Quan Zang\",\"doi\":\"10.1021/jacs.5c09304\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Achieving efficient near-infrared (NIR) luminescence in atomically precise gold nanoclusters is challenging due to the strong vibrational freedom of the gold core. Herein, we synthesized two gold nanoclusters, [Au11(PPh3)8Cl2]Cl (Au11-1) and Au11(PPh3)7Cl3 (Au11-2), with comparable initial NIR photoluminescence quantum yields (PLQY, 0.3% and 0.32%, respectively), and systematically investigated their NIR piezoluminescence behaviors based on the hydrostatic pressure effect. Under high pressure, Au11-1 exhibits a significant NIR piezoluminescence enhancement. When the pressure increases to 3.6 GPa, the NIR-PLQY of Au11-1 amplifies from the initial 0.3% to 75.6%, which is the highest PLQY reported for solid-state gold nanoclusters. However, Au11-2 exhibits only monotonic pressure-induced luminescence quenching under compression. In situ high-pressure angle-dispersive X-ray diffraction experiments and theoretical calculations confirm the existence of distinct anisotropic compressions in Au11-1 and Au11-2, which induce differential structural distortion of the gold core. The faster shrinkage along the a-axis exacerbates the structural distortion of the Au11-1 core, whereas the more rapid compression along the b-axis in Au11-2 suppresses the structural distortion of the gold core. High-pressure femtosecond transient absorption and Raman spectra synergistically demonstrate that pressure-driven directional structural distortion significantly suppresses nonradiative losses caused by low-frequency vibrations of the Au11-1 core along the a-axis, resulting in NIR piezoluminescence enhancement of Au11-1. Our study deeply reveals the intrinsic correlation between NIR-PLQY and metal core vibration relaxation at the atomic scale and provides a new approach to design and develop high-performance NIR luminescent materials.\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"13 1\",\"pages\":\"\"},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2025-07-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.5c09304\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.5c09304","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Pressure-Activated Efficient Near-Infrared Luminescence in Atomically Precise Gold Nanoclusters.
Achieving efficient near-infrared (NIR) luminescence in atomically precise gold nanoclusters is challenging due to the strong vibrational freedom of the gold core. Herein, we synthesized two gold nanoclusters, [Au11(PPh3)8Cl2]Cl (Au11-1) and Au11(PPh3)7Cl3 (Au11-2), with comparable initial NIR photoluminescence quantum yields (PLQY, 0.3% and 0.32%, respectively), and systematically investigated their NIR piezoluminescence behaviors based on the hydrostatic pressure effect. Under high pressure, Au11-1 exhibits a significant NIR piezoluminescence enhancement. When the pressure increases to 3.6 GPa, the NIR-PLQY of Au11-1 amplifies from the initial 0.3% to 75.6%, which is the highest PLQY reported for solid-state gold nanoclusters. However, Au11-2 exhibits only monotonic pressure-induced luminescence quenching under compression. In situ high-pressure angle-dispersive X-ray diffraction experiments and theoretical calculations confirm the existence of distinct anisotropic compressions in Au11-1 and Au11-2, which induce differential structural distortion of the gold core. The faster shrinkage along the a-axis exacerbates the structural distortion of the Au11-1 core, whereas the more rapid compression along the b-axis in Au11-2 suppresses the structural distortion of the gold core. High-pressure femtosecond transient absorption and Raman spectra synergistically demonstrate that pressure-driven directional structural distortion significantly suppresses nonradiative losses caused by low-frequency vibrations of the Au11-1 core along the a-axis, resulting in NIR piezoluminescence enhancement of Au11-1. Our study deeply reveals the intrinsic correlation between NIR-PLQY and metal core vibration relaxation at the atomic scale and provides a new approach to design and develop high-performance NIR luminescent materials.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.