当前位置: X-MOL 学术Chem. Phys. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Water-soluble phosphine-protected Au9 clusters: Electronic structures and nuclearity conversion via phase transfer
Chemical Physics ( IF 2.3 ) Pub Date : 2017-07-11 00:00:00 , DOI: 10.1016/j.chemphys.2017.07.001
Hiroshi Yao , Shuhei Tsubota

In this article, isolation, exploration of electronic structures, and nuclearity conversion of water-soluble triphenylphosphine monosulfonate (TPPS)-protected nonagold (Au9) clusters are outlined. The Au9 clusters are obtained by the reduction of solutions containing TPPS and HAuCl4 and subsequent electrophoretic fractionation. Mass spectrometry and elemental analysis reveal the formation of [Au9(TPPS)8]5– nonagold cluster. UV-vis absorption and magnetic circular dichroism (MCD) spectra of aqueous [Au9(TPPS)8]5– are quite similar to those of [Au9(PPh3)8]3+ in organic solvent, so the solution-phase structures are likely similar for both systems. Simultaneous deconvolution analysis of absorption and MCD spectra demonstrates the presence of some weak electronic transitions that are essentially unresolved in the UV-vis absorption. Quantum chemical calculations for a model compound [Au9(PH3)8]3+ show that the possible (solution-phase) skeletal structure of the nonagold cluster has D2h core symmetry rather than C4-symmetrical centered crown conformation, which is known as the crystal form of the Au9 compound. Moreover, we find a new nuclearity conversion route from Au9 to Au8; that is, phase transfer of aqueous [Au9(TPPS)8]5– into chloroform using tetraoctylammonium bromide yields [Au8(TPPS)8]6– clusters in the absence of excess phosphine.

中文翻译:

水溶性膦保护的Au 9团簇:电子结构和通过相转移的核转化

在本文中,概述了水溶性三苯膦单磺酸盐(TPPS)保护的九联(Au 9)簇的分离,电子结构的探索和核转化。通过还原含有TPPS和HAuCl 4的溶液,然后进行电泳分离,可获得Au 9团簇。质谱和元素分析揭示了[Au 9(TPPS)8 ] 5–非金簇的形成。[Au 9(TPPS)8 ] 5–水溶液的紫外可见吸收光谱和磁圆二色性(MCD)光谱与[Au 9(PPh 3)]的光谱非常相似8 ] 3+在有机溶剂中,因此两种系统的溶液相结构可能相似。吸收光谱和MCD光谱的同时解卷积分析表明,存在一些弱的电子跃迁,这些跃迁在UV-vis吸收中基本上无法解析。对模型化合物[Au 9(PH 38 ] 3+的量子化学计算表明,非金簇的可能的(溶液相)骨架结构具有D 2h核心对称性,而不是C 4对称的中心冠构象,这是被称为Au 9的晶体形式化合物。此外,我们发现了一条从Au 9到Au 8的新核转化途径。就是说,在没有过量膦的情况下,使用四辛基溴化铵将[Au 9(TPPS)8 ] 5–水溶液相转移到氯仿中,得到[Au 8(TPPS)8 ] 6–簇。
更新日期:2017-07-11
down
wechat
bug