{"title":"Transformation of [Au25(4-PyET)18]– into [Au20(4-PyET)14CN]– Induced by Atmospheric Pressure Plasma Irradiation in Methanol","authors":"Lewei Wang, Kiichirou Koyasu, Tatsuya Tsukuda","doi":"10.1007/s10876-025-02859-2","DOIUrl":null,"url":null,"abstract":"<div><p>The transformation of well-characterized, ligand-protected gold nanoclusters (AuNCs) is a promising approach for the targeted synthesis of novel AuNCs. Our group has previously reported that [MAu<sub>8</sub>(PPh<sub>3</sub>)<sub>8</sub>]<sup>2+</sup> (M = Au<sup>+</sup>, Pd) in methanol was transformed into unprecedented NCs by incorporating one or two AuCN units through atmospheric pressure plasma (APP) irradiation. In order to broaden the scope of the APP-based transformation, the reaction on a prototypical thiolate-protected AuNCs [Au<sub>25</sub>(SR)<sub>18</sub>]<sup>–</sup> was studied. APP irradiation of [Au<sub>25</sub>(4-PyET)<sub>18</sub>]<sup>–</sup> (4-PyET = 4-pyridineethanethiol) resulted in a transformation to [Au<sub>20</sub>(4-PyET)<sub>14</sub>CN]<sup>–</sup>, accompanied by oxidation, while [Au<sub>25</sub>(<i>p</i>-MBA)<sub>18</sub>]<sup>–</sup> (<i>p</i>-MBA = 4-mercaptobenzoic acid) was transformed into larger plasmonic Au nanoparticles. The geometric and electronic structures of a simplified model [Au<sub>20</sub>(SCH<sub>3</sub>)<sub>14</sub>CN]<sup>–</sup> were investigated by density functional theory (DFT) calculations. It was proposed that [Au<sub>20</sub>(SCH<sub>3</sub>)<sub>14</sub>CN]<sup>–</sup> has an oblate Au<sub>10</sub> superatomic core protected by two Au<sub>2</sub>(4-PyET)<sub>3</sub> and two Au<sub>3</sub>(4-PyET)<sub>4</sub> oligomers.</p></div>","PeriodicalId":618,"journal":{"name":"Journal of Cluster Science","volume":"36 4","pages":""},"PeriodicalIF":3.6000,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10876-025-02859-2.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Cluster Science","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10876-025-02859-2","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The transformation of well-characterized, ligand-protected gold nanoclusters (AuNCs) is a promising approach for the targeted synthesis of novel AuNCs. Our group has previously reported that [MAu8(PPh3)8]2+ (M = Au+, Pd) in methanol was transformed into unprecedented NCs by incorporating one or two AuCN units through atmospheric pressure plasma (APP) irradiation. In order to broaden the scope of the APP-based transformation, the reaction on a prototypical thiolate-protected AuNCs [Au25(SR)18]– was studied. APP irradiation of [Au25(4-PyET)18]– (4-PyET = 4-pyridineethanethiol) resulted in a transformation to [Au20(4-PyET)14CN]–, accompanied by oxidation, while [Au25(p-MBA)18]– (p-MBA = 4-mercaptobenzoic acid) was transformed into larger plasmonic Au nanoparticles. The geometric and electronic structures of a simplified model [Au20(SCH3)14CN]– were investigated by density functional theory (DFT) calculations. It was proposed that [Au20(SCH3)14CN]– has an oblate Au10 superatomic core protected by two Au2(4-PyET)3 and two Au3(4-PyET)4 oligomers.
期刊介绍:
The journal publishes the following types of papers: (a) original and important research;
(b) authoritative comprehensive reviews or short overviews of topics of current
interest; (c) brief but urgent communications on new significant research; and (d)
commentaries intended to foster the exchange of innovative or provocative ideas, and
to encourage dialogue, amongst researchers working in different cluster
disciplines.