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一锅法合成的由单硫醇 - 乙酰 -(-)-青霉胺保护的水溶性手性银簇合物。

Water-Soluble Chiral Ag Clusters Protected by Monothiol -Acetyl-()-penicillamine Synthesized in One Pot.

作者信息

Nakanishi Tatsuya, Yao Hiroshi

机构信息

Division of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8507, Japan.

出版信息

J Phys Chem Lett. 2023 Nov 16;14(45):10285-10292. doi: 10.1021/acs.jpclett.3c02780. Epub 2023 Nov 9.

Abstract

Despite significant advances in atomically precise Au clusters with chirality, Ag clusters with the relevant features are still less explored. In this study, we report successful synthesis of chiral Ag clusters protected by water-soluble in one pot, which is carried out by reducing Ag ions in the presence of -acetyl-()-penicillamine (-NAP) and triphenylphosphine (TPP) at 10 °C, yielding the Ag(-NAP) cluster. The obtained cluster is isolable as a solid-state powder. Optical absorption of Ag(-NAP) is almost identical with that of Ag(-DHLA), where DHLA denotes α-dihydrolipoic acid, and magnetic circular dichroism (MCD) results support the similarity of their electronic structures. The anisotropy factor of Ag(-NAP) is comparable to or larger than that of Ag(-DHLA), suggesting that the surface shell structure of Ag(-NAP) is inherently chiral, as has been observed for Ag(-DHLA). Then the use of enantiopure NAP would preferentially lead to a one-handed atomic arrangement in the clusters.

摘要

尽管在手性原子精确金团簇方面取得了重大进展,但具有相关特征的银团簇仍较少被研究。在本研究中,我们报告了在一个反应釜中成功合成了由水溶性物质保护的手性银团簇,这是通过在10℃下在乙酰基-(-)-青霉胺(-NAP)和三苯基膦(TPP)存在下还原银离子来实现的,得到了Ag(-NAP)团簇。所获得的团簇可作为固态粉末分离出来。Ag(-NAP)的光吸收与Ag(-DHLA)几乎相同,其中DHLA表示α-二氢硫辛酸,磁圆二色性(MCD)结果支持了它们电子结构的相似性。Ag(-NAP)的各向异性因子与Ag(-DHLA)相当或更大,这表明Ag(-NAP)的表面壳层结构本质上是手性的,正如在Ag(-DHLA)中所观察到的那样。然后,使用对映体纯的NAP将优先导致团簇中单手原子排列。

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