Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis
Abstract The elucidation of hierarchical assembly structure of metal nanoclusters is of fundamental importance in the context of bottom‐up fabrication and functionalization. While recent studies have provided valuable insights into the multiscale assembly patterns of gold or silver‐based nanocluster...
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Wiley
2025-01-01
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| Online Access: | https://doi.org/10.1002/agt2.651 |
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| author | Xueli Sun Yuchen Wang Qingyuan Wu Ying‐Zi Han Xuekun Gong Xiongkai Tang Christine M. Aikens Hui Shen Nanfeng Zheng |
| author_facet | Xueli Sun Yuchen Wang Qingyuan Wu Ying‐Zi Han Xuekun Gong Xiongkai Tang Christine M. Aikens Hui Shen Nanfeng Zheng |
| author_sort | Xueli Sun |
| collection | DOAJ |
| description | Abstract The elucidation of hierarchical assembly structure of metal nanoclusters is of fundamental importance in the context of bottom‐up fabrication and functionalization. While recent studies have provided valuable insights into the multiscale assembly patterns of gold or silver‐based nanoclusters, the success in achieving similar results for copper analogues has been notably limited. Herein, by virtue of a slow‐ligand‐release strategy, a copper nanocluster denoted as [Cu66Cl8(PPh3)8(SC2H5)32H24](SbF6)2 was synthesized, resulting in the formation of fresh hierarchical assembly structures in one‐pot. The arrangement of the metal atoms within the cluster reveals an orderly of 16 Cu4 squares, representing a rare copper nanocluster comprising square motifs. Additionally, the ligands (phosphine, thiolate, and halide) coordinate to the surface of the cluster in a regiospecific manner, displaying square patterns as well. The self‐assembly facilitated by the C‐H···F interaction between the cluster moieties and SbF6− anions further induces the formation of three‐dimensional cubes and eventually large nanocrystals. Density functional theoretical (DFT) calculations reveal that hydride atoms with low chemical shifts typically exhibit short Cu‐H distances. The cluster demonstrates moderate stability and high catalytic activity in the chemoselective hydrogenation of cyclohexanone under mild conditions. |
| format | Article |
| id | doaj-art-a5528c8960ea4aa9880b583212546ee6 |
| institution | Kabale University |
| issn | 2692-4560 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley |
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| spelling | doaj-art-a5528c8960ea4aa9880b583212546ee62025-01-21T08:57:07ZengWileyAggregate2692-45602025-01-0161n/an/a10.1002/agt2.651Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysisXueli Sun0Yuchen Wang1Qingyuan Wu2Ying‐Zi Han3Xuekun Gong4Xiongkai Tang5Christine M. Aikens6Hui Shen7Nanfeng Zheng8College of Energy Materials and Chemistry Inner Mongolia University Hohhot ChinaDepartment of Chemistry Kansas State University Manhattan Kansas USANew Cornerstone Science Laboratory State Key Laboratory for Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials College of Chemistry and Chemical Engineering Xiamen University Xiamen ChinaNew Cornerstone Science Laboratory State Key Laboratory for Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials College of Chemistry and Chemical Engineering Xiamen University Xiamen ChinaCollege of Energy Materials and Chemistry Inner Mongolia University Hohhot ChinaNew Cornerstone Science Laboratory State Key Laboratory for Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials College of Chemistry and Chemical Engineering Xiamen University Xiamen ChinaDepartment of Chemistry Kansas State University Manhattan Kansas USACollege of Energy Materials and Chemistry Inner Mongolia University Hohhot ChinaNew Cornerstone Science Laboratory State Key Laboratory for Physical Chemistry of Solid Surfaces Collaborative Innovation Center of Chemistry for Energy Materials and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials College of Chemistry and Chemical Engineering Xiamen University Xiamen ChinaAbstract The elucidation of hierarchical assembly structure of metal nanoclusters is of fundamental importance in the context of bottom‐up fabrication and functionalization. While recent studies have provided valuable insights into the multiscale assembly patterns of gold or silver‐based nanoclusters, the success in achieving similar results for copper analogues has been notably limited. Herein, by virtue of a slow‐ligand‐release strategy, a copper nanocluster denoted as [Cu66Cl8(PPh3)8(SC2H5)32H24](SbF6)2 was synthesized, resulting in the formation of fresh hierarchical assembly structures in one‐pot. The arrangement of the metal atoms within the cluster reveals an orderly of 16 Cu4 squares, representing a rare copper nanocluster comprising square motifs. Additionally, the ligands (phosphine, thiolate, and halide) coordinate to the surface of the cluster in a regiospecific manner, displaying square patterns as well. The self‐assembly facilitated by the C‐H···F interaction between the cluster moieties and SbF6− anions further induces the formation of three‐dimensional cubes and eventually large nanocrystals. Density functional theoretical (DFT) calculations reveal that hydride atoms with low chemical shifts typically exhibit short Cu‐H distances. The cluster demonstrates moderate stability and high catalytic activity in the chemoselective hydrogenation of cyclohexanone under mild conditions.https://doi.org/10.1002/agt2.651assemblycatalytic reactionscopperligandsmetal clusters |
| spellingShingle | Xueli Sun Yuchen Wang Qingyuan Wu Ying‐Zi Han Xuekun Gong Xiongkai Tang Christine M. Aikens Hui Shen Nanfeng Zheng Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis Aggregate assembly catalytic reactions copper ligands metal clusters |
| title | Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis |
| title_full | Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis |
| title_fullStr | Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis |
| title_full_unstemmed | Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis |
| title_short | Cu66 nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis |
| title_sort | cu66 nanoclusters from hierarchical square motifs synthesis assembly and catalysis |
| topic | assembly catalytic reactions copper ligands metal clusters |
| url | https://doi.org/10.1002/agt2.651 |
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