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A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all-alkynyl-protected gold nanoclusters. Direct reduction of dpa-passivated precursor Au-dpa (Hdpa=2,2'-dipyridylamine) in one-pot under ambient conditions gives a series of clusters including Au(C≡CR) (R=-CH-2-F), Au(C≡CR), Au(C≡CR), Au(C≡CR), and Au(C≡CR). These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au(C≡CR) is revealed, which presents important information for understanding the structure of the mysterious Au nanoclusters. Theoretical calculations indicated Au(C≡CR) has a smaller HOMO-LUMO gap than Au(S-CH-4-CH). This facile and reliable synthetic approach will greatly accelerate further studies on all-alkynyl-protected gold nanoclusters.
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http://dx.doi.org/10.1002/chem.202401094 | DOI Listing |
Small
May 2025
Department of Chemistry, Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education), Tsinghua University, Beijing, 100084, P. R. China.
Isomerization of nanoclusters is helpful for understanding the relationships between structures and properties. Surface-protecting ligands play a crucial role in controlling the atomic packing mode of the inner core. The synthesis and total structural determination of the all alkynyl-protected gold nanocluster (NEtCHCl)[Au(C≡CCHPh)] (Au-1) are reported.
View Article and Find Full Text PDFChemistry
July 2024
Department of Chemistry, Tsinghua University, 100084, Beijing, P. R. China.
A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all-alkynyl-protected gold nanoclusters. Direct reduction of dpa-passivated precursor Au-dpa (Hdpa=2,2'-dipyridylamine) in one-pot under ambient conditions gives a series of clusters including Au(C≡CR) (R=-CH-2-F), Au(C≡CR), Au(C≡CR), Au(C≡CR), and Au(C≡CR). These clusters can be well separated via column chromatography.
View Article and Find Full Text PDFSci Adv
March 2023
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, People's Republic of China.
Intrinsic dual-emission (DE) of gold nanoclusters in the near-infrared (NIR) are fascinating for fundamental importance and practical applications, but their synthesis remains a formidable challenge and sophisticated excited-state processes make elucidating DE mechanisms much more arduous. Here, we report an all-alkynyl-protected gold nanocluster, , showing a prolate Au tri-octahedral kernel surrounded by two Au(CZ-PrA) dimers, four Au(CZ-PrA) monomers, and two CZ-PrA bridges. exhibits distinguished photophysical properties including NIR DE at 820 and 940 nm, microsecond radiative relaxation, and 6.
View Article and Find Full Text PDFJ Am Chem Soc
October 2021
Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084, P.R. China.
The boundary between molecular and metallic gold nanoclusters is of special interest. The difficulty in obtaining atomically precise nanoclusters larger than 2 nm limits the determination of such a boundary. The synthesis and total structural determination of the largest all-alkynyl-protected gold nanocluster (PhP)[Au(C≡CR)] (R = 4-CFCH-) () are reported.
View Article and Find Full Text PDFJ Am Chem Soc
October 2020
Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 10084, PR China.
Great attention has been paid to nanoclusters having face-centered-cubic (fcc) metal kernels, because of the similarity of metal packing to that of bulk gold. So far, there is no precedent example of an all-alkynyl-protected fcc gold nanocluster with more than 100 gold atoms. We report the synthesis and total structure determination of an alkynyl-protected gold nanocluster [NEtH][Au(CFCHC≡C)] ().
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