Abdul Mannan Butt, Abhijit Nag, Praveen B. Managutti, Sharmarke Mohamed, Faisal AlMarzooqi, Ahsanulhaq Qurashi
{"title":"两种（Cu14和Cu41）原子精密铜纳米团簇的方法诱导异构和浓度介导分离","authors":"Abdul Mannan Butt, Abhijit Nag, Praveen B. Managutti, Sharmarke Mohamed, Faisal AlMarzooqi, Ahsanulhaq Qurashi","doi":"10.1002/cmtd.202400031","DOIUrl":null,"url":null,"abstract":"<p>Ligand-protected atomically precise metal nanoclusters (MNCs) have attracted peculiar interest not only for their distinct molecular structure but also for their unique physiochemical properties, providing an ideal platform for developing structure-activity correlation at the atomic level. In this work, we have presented the isolation of two nanoclusters (NCs) [Cu<sub>14</sub>H<sub>10</sub>(DMBT)<sub>3</sub>(PPh<sub>3</sub>)<sub>8</sub>][BF<sub>4</sub>] (<b>Cu<sub>14</sub></b>) and [Cu<sub>41</sub>H<sub>21</sub>Cl<sub>8</sub>(DMBT)<sub>12</sub>(PPh<sub>3</sub>)<sub>6</sub>] (<b>Cu<sub>41</sub></b>) [DMBT=2,4-dimethylbenzenethiol and PPh<sub>3</sub>=Triphenylphosphine] upon manipulating the concentration of thiol ligand. A correlation between thiolate ligand's concentration and product selectivity was noticed. Further, the presence of R and S isomerism was observed in Cu<sub>14</sub> unit cell. Single Crystal X-ray Diffraction (SC-XRD) data revealed that Cu<sub>14</sub> crystallized in the cubic space group <i>Pa</i>-3, while Cu<sub>41</sub> in hexagonal space group <i>P</i>6<sub>3</sub>/<i>m</i>. The crystal structure of Cu<sub>14</sub> and Cu<sub>41</sub> NCs were supported using high resolution electrospray mass spectrometry (ESI MS) and other spectroscopic approaches. We believe this study will serve as a guide for controllable synthesis of MNCs.</p>","PeriodicalId":72562,"journal":{"name":"Chemistry methods : new approaches to solving problems in chemistry","volume":"5 4","pages":""},"PeriodicalIF":6.1000,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400031","citationCount":"0","resultStr":"{\"title\":\"Method-Induced Isomerism and Concentration Mediated Isolation of Two (Cu14 and Cu41) Atomically Precise Copper Nanoclusters\",\"authors\":\"Abdul Mannan Butt, Abhijit Nag, Praveen B. Managutti, Sharmarke Mohamed, Faisal AlMarzooqi, Ahsanulhaq Qurashi\",\"doi\":\"10.1002/cmtd.202400031\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Ligand-protected atomically precise metal nanoclusters (MNCs) have attracted peculiar interest not only for their distinct molecular structure but also for their unique physiochemical properties, providing an ideal platform for developing structure-activity correlation at the atomic level. In this work, we have presented the isolation of two nanoclusters (NCs) [Cu<sub>14</sub>H<sub>10</sub>(DMBT)<sub>3</sub>(PPh<sub>3</sub>)<sub>8</sub>][BF<sub>4</sub>] (<b>Cu<sub>14</sub></b>) and [Cu<sub>41</sub>H<sub>21</sub>Cl<sub>8</sub>(DMBT)<sub>12</sub>(PPh<sub>3</sub>)<sub>6</sub>] (<b>Cu<sub>41</sub></b>) [DMBT=2,4-dimethylbenzenethiol and PPh<sub>3</sub>=Triphenylphosphine] upon manipulating the concentration of thiol ligand. A correlation between thiolate ligand's concentration and product selectivity was noticed. Further, the presence of R and S isomerism was observed in Cu<sub>14</sub> unit cell. Single Crystal X-ray Diffraction (SC-XRD) data revealed that Cu<sub>14</sub> crystallized in the cubic space group <i>Pa</i>-3, while Cu<sub>41</sub> in hexagonal space group <i>P</i>6<sub>3</sub>/<i>m</i>. The crystal structure of Cu<sub>14</sub> and Cu<sub>41</sub> NCs were supported using high resolution electrospray mass spectrometry (ESI MS) and other spectroscopic approaches. We believe this study will serve as a guide for controllable synthesis of MNCs.</p>\",\"PeriodicalId\":72562,\"journal\":{\"name\":\"Chemistry methods : new approaches to solving problems in chemistry\",\"volume\":\"5 4\",\"pages\":\"\"},\"PeriodicalIF\":6.1000,\"publicationDate\":\"2025-03-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cmtd.202400031\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry methods : new approaches to solving problems in chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/cmtd.202400031\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry methods : new approaches to solving problems in chemistry","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/cmtd.202400031","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Method-Induced Isomerism and Concentration Mediated Isolation of Two (Cu14 and Cu41) Atomically Precise Copper Nanoclusters
Ligand-protected atomically precise metal nanoclusters (MNCs) have attracted peculiar interest not only for their distinct molecular structure but also for their unique physiochemical properties, providing an ideal platform for developing structure-activity correlation at the atomic level. In this work, we have presented the isolation of two nanoclusters (NCs) [Cu14H10(DMBT)3(PPh3)8][BF4] (Cu14) and [Cu41H21Cl8(DMBT)12(PPh3)6] (Cu41) [DMBT=2,4-dimethylbenzenethiol and PPh3=Triphenylphosphine] upon manipulating the concentration of thiol ligand. A correlation between thiolate ligand's concentration and product selectivity was noticed. Further, the presence of R and S isomerism was observed in Cu14 unit cell. Single Crystal X-ray Diffraction (SC-XRD) data revealed that Cu14 crystallized in the cubic space group Pa-3, while Cu41 in hexagonal space group P63/m. The crystal structure of Cu14 and Cu41 NCs were supported using high resolution electrospray mass spectrometry (ESI MS) and other spectroscopic approaches. We believe this study will serve as a guide for controllable synthesis of MNCs.
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