Jun-Ling Jin, Sheng-Fa Zhang, Jun-Jie Fang, Yang-Lin Shen, Yun-Peng Xie and Xing Lu
{"title":"苯乙炔稳定剂辅助组装银(I)-铜(I)双金属硫醇复合物","authors":"Jun-Ling Jin, Sheng-Fa Zhang, Jun-Jie Fang, Yang-Lin Shen, Yun-Peng Xie and Xing Lu","doi":"10.1039/D4DT02753A","DOIUrl":null,"url":null,"abstract":"<p >Ag<small><sup>I</sup></small>/Cu<small><sup>I</sup></small> bimetallic clusters have been widely reported, but synthesis of such clusters <em>via</em> simple self-assembly of heterometallic ions in air remains challenging due to the susceptibility of Cu<small><sup>I</sup></small> ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CH<small><sub>3</sub></small>CN)<small><sub>4</sub></small>]PF<small><sub>6</sub></small> in conjunction with the (<small><sup><em>i</em></sup></small>PrSAg)<small><sub><em>n</em></sub></small> polymer to form Ag(<small>I</small>)–Cu(<small>I</small>) oligomer precursors, serving as the starting point for constructing a new [Ag<small><sub>11−<em>x</em></sub></small>Cu<small><sub><em>x</em></sub></small>(<small><sup><em>i</em></sup></small>PrS)<small><sub>9</sub></small>(DPPM)<small><sub>3</sub></small>](PF<small><sub>6</sub></small>)<small><sub>2</sub></small> cluster (DPPM = bis(diphenylphosphino)methane, <strong>Ag<small><sub>11−<em>x</em></sub></small>Cu<small><sub><em>x</em></sub></small></strong>, <em>x</em> = 5–9). When the (<small><sup><em>i</em></sup></small>PrSAg)<small><sub><em>n</em></sub></small> precursor was replaced by (<small><sup><em>t</em></sup></small>BuSAg)<small><sub><em>n</em></sub></small>, another cluster [Ag<small><sub>21</sub></small>Cu<small><sub>4</sub></small>S<small><sub>2</sub></small>(<small><sup><em>t</em></sup></small>BuS)<small><sub>18</sub></small>(CH<small><sub>3</sub></small>CN)<small><sub>4</sub></small>](CH<small><sub>3</sub></small>OH)<small><sub>2</sub></small>(H<small><sub>3</sub></small>O)(PF<small><sub>6</sub></small>)<small><sub>4</sub></small> (<strong>Ag<small><sub>21</sub></small>Cu<small><sub>4</sub></small></strong>) was obtained. By combining crystallographic data and electrospray ionization mass spectrometry (ESI-MS) results, the compositions and structures of these two new clusters were determined. Additionally, the optical physical properties of the luminescent <strong>Ag<small><sub>11−<em>x</em></sub></small>Cu<small><sub><em>x</em></sub></small></strong> were investigated, showing red phosphorescence emission in both solid-state and solution phases. The solid-state phosphorescence quantum yield (QY) is 8%, with a lifetime of 7.2 μs. These findings suggest that phenylacetylene auxiliary ligands can effectively stabilize Cu<small><sup>I</sup></small> ions and guide the assembly of silver-copper bimetallic thiolate motifs into new compounds under ambient conditions.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 3","pages":" 1270-1275"},"PeriodicalIF":3.3000,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Assembly of silver(i)–copper(i) bimetallic thiolate complexes assisted by phenylacetylene stabilizers†\",\"authors\":\"Jun-Ling Jin, Sheng-Fa Zhang, Jun-Jie Fang, Yang-Lin Shen, Yun-Peng Xie and Xing Lu\",\"doi\":\"10.1039/D4DT02753A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Ag<small><sup>I</sup></small>/Cu<small><sup>I</sup></small> bimetallic clusters have been widely reported, but synthesis of such clusters <em>via</em> simple self-assembly of heterometallic ions in air remains challenging due to the susceptibility of Cu<small><sup>I</sup></small> ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CH<small><sub>3</sub></small>CN)<small><sub>4</sub></small>]PF<small><sub>6</sub></small> in conjunction with the (<small><sup><em>i</em></sup></small>PrSAg)<small><sub><em>n</em></sub></small> polymer to form Ag(<small>I</small>)–Cu(<small>I</small>) oligomer precursors, serving as the starting point for constructing a new [Ag<small><sub>11−<em>x</em></sub></small>Cu<small><sub><em>x</em></sub></small>(<small><sup><em>i</em></sup></small>PrS)<small><sub>9</sub></small>(DPPM)<small><sub>3</sub></small>](PF<small><sub>6</sub></small>)<small><sub>2</sub></small> cluster (DPPM = bis(diphenylphosphino)methane, <strong>Ag<small><sub>11−<em>x</em></sub></small>Cu<small><sub><em>x</em></sub></small></strong>, <em>x</em> = 5–9). When the (<small><sup><em>i</em></sup></small>PrSAg)<small><sub><em>n</em></sub></small> precursor was replaced by (<small><sup><em>t</em></sup></small>BuSAg)<small><sub><em>n</em></sub></small>, another cluster [Ag<small><sub>21</sub></small>Cu<small><sub>4</sub></small>S<small><sub>2</sub></small>(<small><sup><em>t</em></sup></small>BuS)<small><sub>18</sub></small>(CH<small><sub>3</sub></small>CN)<small><sub>4</sub></small>](CH<small><sub>3</sub></small>OH)<small><sub>2</sub></small>(H<small><sub>3</sub></small>O)(PF<small><sub>6</sub></small>)<small><sub>4</sub></small> (<strong>Ag<small><sub>21</sub></small>Cu<small><sub>4</sub></small></strong>) was obtained. By combining crystallographic data and electrospray ionization mass spectrometry (ESI-MS) results, the compositions and structures of these two new clusters were determined. Additionally, the optical physical properties of the luminescent <strong>Ag<small><sub>11−<em>x</em></sub></small>Cu<small><sub><em>x</em></sub></small></strong> were investigated, showing red phosphorescence emission in both solid-state and solution phases. The solid-state phosphorescence quantum yield (QY) is 8%, with a lifetime of 7.2 μs. These findings suggest that phenylacetylene auxiliary ligands can effectively stabilize Cu<small><sup>I</sup></small> ions and guide the assembly of silver-copper bimetallic thiolate motifs into new compounds under ambient conditions.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 3\",\"pages\":\" 1270-1275\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2024-11-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02753a\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02753a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Assembly of silver(i)–copper(i) bimetallic thiolate complexes assisted by phenylacetylene stabilizers†
AgI/CuI bimetallic clusters have been widely reported, but synthesis of such clusters via simple self-assembly of heterometallic ions in air remains challenging due to the susceptibility of CuI ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CH3CN)4]PF6 in conjunction with the (iPrSAg)n polymer to form Ag(I)–Cu(I) oligomer precursors, serving as the starting point for constructing a new [Ag11−xCux(iPrS)9(DPPM)3](PF6)2 cluster (DPPM = bis(diphenylphosphino)methane, Ag11−xCux, x = 5–9). When the (iPrSAg)n precursor was replaced by (tBuSAg)n, another cluster [Ag21Cu4S2(tBuS)18(CH3CN)4](CH3OH)2(H3O)(PF6)4 (Ag21Cu4) was obtained. By combining crystallographic data and electrospray ionization mass spectrometry (ESI-MS) results, the compositions and structures of these two new clusters were determined. Additionally, the optical physical properties of the luminescent Ag11−xCux were investigated, showing red phosphorescence emission in both solid-state and solution phases. The solid-state phosphorescence quantum yield (QY) is 8%, with a lifetime of 7.2 μs. These findings suggest that phenylacetylene auxiliary ligands can effectively stabilize CuI ions and guide the assembly of silver-copper bimetallic thiolate motifs into new compounds under ambient conditions.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.