Isomer Structural Transformation in Au-Cu Alloy Nanoclusters: Water Ripple-Like Transfer of Thiol Ligands
Isomer Structural Transformation in Au-Cu Alloy Nanoclusters: Water Ripple-Like Transfer of Thiol Ligands
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Au-Cu合金纳米团簇中的异构体结构转变：硫醇配体的水波纹样转移
DOI：
10.1002/ppsc.201800494
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发表时间：
2019
影响因子：
2.7
通讯作者：
Zhu Manzhou
中科院分区：
文献类型：
--
作者：
Yu Wei;Hu Daqiao;Xiong Lin;Li Yangfeng;Kang Xi;Chen Shuang;Wang Shuxin;Pei Yong;Zhu Manzhou
在贵金属纳米团簇中观察到了结构异构化现象，但对这一过程的机理研究却鲜有报道。其中，通过用双膦配体取代膦配体，成功地打破了Au2Cu6(PPh_3)_2(SADM)_6纳米团簇的高度对称性，得到了手性排列的[Au_4Cu4(L_1)_2(SADM)_5]Br(其中，L_1是双(二苯基膦)甲烷，DPPM)纳米团簇。这个新获得的纳米团簇在晶胞中总共包含四个异构体。有趣的是，这些异构体在溶液中发生了快速的同象，通过1H-1H COSY光谱证实了这一点。密度泛函理论计算表明，硫醇配体的水波纹状转移是由纳米团簇的类质同构引起的。
Structure isomerism is observed in noble metal nanoclusters; however, the mechanism study of this process is rarely reported. Herein, by using the biphosphine ligands instead of phosphine ligands, the high symmetry of the Au2Cu6(PPh3)2(SAdm)6nanocluster is successfully broken and [Au4Cu4(L1)2(SAdm)5]Br (where, L1is bis(diphenylphosphine)methane, DPPM) nanocluster is obtained with chiral arrangement. This newly obtained nanocluster contains a total of four isomers in crystal unit cell. Interestingly, these isomers undergo rapid isomorphism in solution, which is confirmed by1H‐1H COSY spectrum. Density functional theory calculations demonstrate that the water ripple–like transfer of the thiol ligands results from the isomorphism of nanoclusters.