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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(38):11652-11655
For the first time total structure determination of homoleptic alkynyl‐protected gold nanoclusters is reported. The nanoclusters are synthesized by direct reduction of PhC≡CAu, to give Au44(PhC≡C)28 and Au36(PhC≡C)24. The Au44 and Au36 nanoclusters have fcc‐type Au36 and Au28 kernels, respectively, as well as surrounding PhC≡C‐Au‐C2(Ph)Au‐C≡CPh dimeric “staples” and simple PhC≡C bridges. The structures of Au44(PhC≡C)28 and Au36(PhC≡C)24 are similar to Au44(SR)28 and Au36(SR)24, but the UV/Vis spectra are different. The protecting ligands influence the electronic structures of nanoclusters significantly. The synthesis of these two alkynyl‐protected gold nanoclusters indicates that a series of gold nanoclusters in the general formula Aux (RC≡C)y as counterparts to Aux (SR)y can be expected. 相似文献
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Peng Yuan Ruihao Chen Xiaomin Zhang Fengjiao Chen Juanzhu Yan Cunfa Sun Daohui Ou Jian Peng Shuichao Lin Zichao Tang Boon K. Teo Lan‐Sun Zheng Nanfeng Zheng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(3):845-849
An effective strategy is developed to synthesize high‐nuclearity Cu clusters, [Cu53(RCOO)10(C≡CtBu)20Cl2H18]+ ( Cu53 ), which is the largest CuI/Cu0 cluster reported to date. Cu powder and Ph2SiH2 are employed as the reducing agents in the synthesis. As revealed by single‐crystal diffraction, Cu53 is arranged as a four‐concentric‐shell Cu3@Cu10Cl2@Cu20@Cu20 structure, possessing an atomic arrangement of concentric M12 icosahedral and M20 dodecahedral shells which popularly occurs in Au/Ag nanoclusters. Surprisingly, Cu53 can be dissolved in diethyl ether and spin coated to form uniform nanoclusters film on organolead halide perovskite. The cluster film can subsequently be converted into high‐quality CuI film via in situ iodination at room temperature. The as‐fabricated CuI film is an excellent hole‐transport layer for fabricating highly stable CuI‐based perovskite solar cells (PSCs) with 14.3 % of efficiency. 相似文献
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Jiao‐Jiao Li Zong‐Jie Guan Zhen Lei Feng Hu Quan‐Ming Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(4):1095-1099
Two homoleptic alkynyl‐protected gold clusters with compositions of Na[Au25(C≡CAr)18] and (Ph4P)[Au25(C≡CAr)18] (Na? 1 and Ph4P? 1 , Ar=3,5‐bis(trifluoromethyl)phenyl) were synthesized via a direct reduction method. 1 is a magic cluster analogous to [Au25(SR)18]? in terms of electron counts and metal‐to‐ligand ratio. Single‐crystal structure analysis reveals that 1 has an identical Au13 kernel to [Au25(SR)18]?, but adopts a distinctly different arrangement of the six peripheral dimer staple motifs. The steric hindrance of alkynyl ligands is responsible for the D3 arrangement of Au25. The introduction of alkynyl also significantly changes the optical absorption features of the nanocluster as supported by DFT calculations. This magic cluster confirms that there is a similar but quite different parallel alkynyl‐protected metal cluster universe in comparison to the thiolated one. 相似文献
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