Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics
The detailed elucidation of structure–property relationships at the molecular level in metal nanoclusters is highly valuable for advancing structure design and optimizing performance. However, effectively manipulating metal nanoclusters’ physical and chemical properties at the single-molecule level...
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| Format: | Article |
| Language: | English |
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Tsinghua University Press
2025-03-01
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| Series: | Polyoxometalates |
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| Online Access: | https://www.sciopen.com/article/10.26599/POM.2024.9140072 |
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| author | Xuekun Gong Zhuang-Hua Liu Qinghua Xu Lin Wang Qingxiang Guo Jian Zhang Qiao-Hong Li Wei-Hui Fang Hui Shen |
| author_facet | Xuekun Gong Zhuang-Hua Liu Qinghua Xu Lin Wang Qingxiang Guo Jian Zhang Qiao-Hong Li Wei-Hui Fang Hui Shen |
| author_sort | Xuekun Gong |
| collection | DOAJ |
| description | The detailed elucidation of structure–property relationships at the molecular level in metal nanoclusters is highly valuable for advancing structure design and optimizing performance. However, effectively manipulating metal nanoclusters’ physical and chemical properties at the single-molecule level remains a significant challenge. Here, we demonstrate that single-molecule chemistry can effectively control the third-order nonlinear optical (NLO) performance of structurally precise copper nanoclusters. We present two analogous clusters, [Cu25(RS)18H10]3− (Cu25) and [Cu26(RS)18H10(PPh3)]2− (Cu26, where RSH is 2-fluorobenzenethiol), whose structures were determined in this study. Both clusters feature a Cu13 core in a centered cuboctahedron configuration with similar shell structures. However, Cu26 includes an additional PPh3Cu+ unit. This single structural difference significantly changes their properties, including optical characteristics and stability. Compared to Cu25, Cu26 exhibits enhanced optical limiting (OL) activity. Theoretical calculations indicate that the substantial electron transfer from the PPh3 ligand to the metal core enhances the NLO performance of Cu26. This study highlights the potential of structurally precise copper nanoclusters as OL materials and advances the understanding of nanoparticulate material fabrication using a single-molecule strategy. |
| format | Article |
| id | doaj-art-6f625015e37b47fb97867bada7a15f32 |
| institution | Kabale University |
| issn | 2957-9821 2957-9503 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Tsinghua University Press |
| record_format | Article |
| series | Polyoxometalates |
| spelling | doaj-art-6f625015e37b47fb97867bada7a15f322025-01-24T08:12:25ZengTsinghua University PressPolyoxometalates2957-98212957-95032025-03-0141914007210.26599/POM.2024.9140072Single-molecule manipulation of copper nanoclusters for modulating nonlinear opticsXuekun Gong0Zhuang-Hua Liu1Qinghua Xu2Lin Wang3Qingxiang Guo4Jian Zhang5Qiao-Hong Li6https://orcid.org/0000-0001-9286-3580Wei-Hui Fang7https://orcid.org/0000-0003-3358-3057Hui Shen8https://orcid.org/0000-0003-4800-437XCollege of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCollege of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCollege of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCollege of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, ChinaThe detailed elucidation of structure–property relationships at the molecular level in metal nanoclusters is highly valuable for advancing structure design and optimizing performance. However, effectively manipulating metal nanoclusters’ physical and chemical properties at the single-molecule level remains a significant challenge. Here, we demonstrate that single-molecule chemistry can effectively control the third-order nonlinear optical (NLO) performance of structurally precise copper nanoclusters. We present two analogous clusters, [Cu25(RS)18H10]3− (Cu25) and [Cu26(RS)18H10(PPh3)]2− (Cu26, where RSH is 2-fluorobenzenethiol), whose structures were determined in this study. Both clusters feature a Cu13 core in a centered cuboctahedron configuration with similar shell structures. However, Cu26 includes an additional PPh3Cu+ unit. This single structural difference significantly changes their properties, including optical characteristics and stability. Compared to Cu25, Cu26 exhibits enhanced optical limiting (OL) activity. Theoretical calculations indicate that the substantial electron transfer from the PPh3 ligand to the metal core enhances the NLO performance of Cu26. This study highlights the potential of structurally precise copper nanoclusters as OL materials and advances the understanding of nanoparticulate material fabrication using a single-molecule strategy.https://www.sciopen.com/article/10.26599/POM.2024.9140072coppercluster compoundsstructurenonlinear opticssingle molecule manipulation |
| spellingShingle | Xuekun Gong Zhuang-Hua Liu Qinghua Xu Lin Wang Qingxiang Guo Jian Zhang Qiao-Hong Li Wei-Hui Fang Hui Shen Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics Polyoxometalates copper cluster compounds structure nonlinear optics single molecule manipulation |
| title | Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics |
| title_full | Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics |
| title_fullStr | Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics |
| title_full_unstemmed | Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics |
| title_short | Single-molecule manipulation of copper nanoclusters for modulating nonlinear optics |
| title_sort | single molecule manipulation of copper nanoclusters for modulating nonlinear optics |
| topic | copper cluster compounds structure nonlinear optics single molecule manipulation |
| url | https://www.sciopen.com/article/10.26599/POM.2024.9140072 |
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