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Atom-Precise Modification of Silver(I) Thiolate Cluster by Shell Ligand Substitution: A New Approach to Generation of Cluster Functionality and Chirality
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2018-01-03 , DOI: 10.1021/jacs.7b12136
Si Li 1 , Xiang-Sha Du 1 , Bing Li 1 , Jia-Yin Wang 1 , Guo-Ping Li 1 , Guang-Gang Gao 2 , Shuang-Quan Zang 1
Affiliation  

To realize the molecular design of new functional silver(I) clusters, a new synthetic approach has been proposed, by which the weakly coordinating ligands NO3- in a Ag20 thiolate cluster precursor can be substituted by carboxylic ligands while keeping its inner core intact. By rational design, novel atom-precise carboxylic or amino acid protected 20-core Ag(I)-thiolate clusters have been demonstrated for the first time. The fluorescence and electrochemical activity of the postmodified Ag20 clusters can be modulated by alrestatin or ferrocenecarboxylic acid substitution. More strikingly, when chiral amino acids were used as postmodified ligands, CD-activity was observed for the Ag20 clusters, unveiling an efficient way to obtain atom-precise chiral silver(I) clusters.

中文翻译:

通过壳配体取代对硫醇银(I)簇进行原子精确修饰:一种生成簇功能和手性的新方法

为了实现新的功能性银(I)簇的分子设计,提出了一种新的合成方法,通过该方法,Ag20 硫醇簇前体中的弱配位配体 NO3- 可以被羧基配体取代,同时保持其内核完整。通过合理的设计,首次证明了新型原子精确羧酸或氨基酸保护的 20 核 Ag(I)-硫醇簇。后修饰的 Ag20 簇的荧光和电化学活性可以通过阿瑞斯汀或二茂铁羧酸取代进行调节。更引人注目的是,当手性氨基酸用作后修饰配体时,观察到 Ag20 簇的 CD 活性,揭示了获得原子精确手性银 (I) 簇的有效方法。
更新日期:2018-01-03
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