| Autor: |
Jia, Tao, Guan, Zong-Jie, Zhang, Chengkai, Zhu, Xiao-Zhao, Chen, Yun-Xin, Zhang, Qian, Yang, Yang, Sun, Di |
| Zdroj: |
Journal of the American Chemical Society; May 2023, Vol. 145 Issue: 18 p10355-10363, 9p |
| Abstrakt: |
Owing to the inherent instability caused by the low Cu(I)/Cu(0) half-cell reduction potential, Cu(0)-containing copper nanoclusters are quite uncommon in comparison to their Ag and Au congeners. Here, a novel eight-electron superatomic copper nanocluster [Cu31(4-MeO-PhC≡C)21(dppe)3](ClO4)2(Cu31, dppe = 1,2-bis(diphenylphosphino)ethane) is presented with total structural characterization. The structural determination reveals that Cu31features an inherent chiral metal core arising from the helical arrangement of two sets of three Cu2units encircling the icosahedral Cu13core, which is further shielded by 4-MeO-PhC≡C–and dppe ligands. Cu31is the first copper nanocluster carrying eight free electrons, which is further corroborated by electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and density functional theory calculations. Interestingly, Cu31demonstrates the first near-infrared (750–950 nm, NIR-I) window absorption and the second near-infrared (1000–1700 nm, NIR-II) window emission, which is exceptional in the copper nanocluster family and endows it with great potential in biological applications. Of note, the 4-methoxy groups providing close contacts with neighboring clusters are crucial for the cluster formation and crystallization, while 2-methoxyphenylacetylene leads only to copper hydride clusters, Cu6Hor Cu32H14. This research not only showcases a new member of copper superatoms but also exemplifies that copper nanoclusters, which are nonluminous in the visible range may emit luminescence in the deep NIR region. |
| Databáze: |
Supplemental Index |
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