Condensed-phase synthesis of atomically precise clusters has become a vital branch of cluster science,where solvents are indispensable in the synthesis process.Herein,by employing the density functional theory(DFT)cal...Condensed-phase synthesis of atomically precise clusters has become a vital branch of cluster science,where solvents are indispensable in the synthesis process.Herein,by employing the density functional theory(DFT)calculations and molecular dynamics(MD)simulations,we demonstrated that polar solvents not only provide an important environment to stabilize clusters,but they can also dramatically alter the electronic property of cluster anions forming novel superhalogen anions.Such a regulation effect was first verified in small model gas-phase pure and doped gold cluster anions,which was further evidenced in a real experimentally synthesized Au18 nanocluster.Different solvation models reveal that the solvent field,which is a noninvasive methodology different from conventional electron-counting rules,can be considered as a novel external field to remarkably increase the electron-binding capability of cluster anions while maintaining their geometrical and electronic structures.Considering the indispensability and convenient availability of the solvents,present findings may boost the potential applications of superatoms in constructing super oxidizers in the condensed phase.展开更多
The Hückel’s rule,Baird’s rule,and electronic shell closure model are classical and well-established concepts in chemistry,which have long been employed in rationalizing the aromaticity/antiaromaticity of organ...The Hückel’s rule,Baird’s rule,and electronic shell closure model are classical and well-established concepts in chemistry,which have long been employed in rationalizing the aromaticity/antiaromaticity of organic species and stability of inorganic clusters.Thus,the observation of unique species featuring properties out of the fundamental frameworks of these rules is challenging but significant and helps in drawing a complete picture of fascinating concepts in chemistry.展开更多
基金supported by the National Natural Science Foundation of China(NSFC,No.92161101)the Taishan Scholars Project of Shandong Province(No.ts201712011)the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032).
文摘Condensed-phase synthesis of atomically precise clusters has become a vital branch of cluster science,where solvents are indispensable in the synthesis process.Herein,by employing the density functional theory(DFT)calculations and molecular dynamics(MD)simulations,we demonstrated that polar solvents not only provide an important environment to stabilize clusters,but they can also dramatically alter the electronic property of cluster anions forming novel superhalogen anions.Such a regulation effect was first verified in small model gas-phase pure and doped gold cluster anions,which was further evidenced in a real experimentally synthesized Au18 nanocluster.Different solvation models reveal that the solvent field,which is a noninvasive methodology different from conventional electron-counting rules,can be considered as a novel external field to remarkably increase the electron-binding capability of cluster anions while maintaining their geometrical and electronic structures.Considering the indispensability and convenient availability of the solvents,present findings may boost the potential applications of superatoms in constructing super oxidizers in the condensed phase.
基金supported by the Taishan Scholars Project of Shandong Province(no.ts201712011)the National Natural Science Foundation of China(NSFC)(nos.21603119 and 21705093)+4 种基金the Natural Science Foundation of Shandong Province(nos.ZR2017BB061 and ZR2016BQ09)the Natural Science Foundation of Jiangsu Province(no.BK20170396)the Project for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province(no.2019KJC025)the Young Scholars Program of Shandong University(YSPSDU)(no.2018WLJH48)the Qilu Youth Scholar Funding of Shandong University,and the Fundamental Research Funds of Shandong University(no.2017TB003).
文摘The Hückel’s rule,Baird’s rule,and electronic shell closure model are classical and well-established concepts in chemistry,which have long been employed in rationalizing the aromaticity/antiaromaticity of organic species and stability of inorganic clusters.Thus,the observation of unique species featuring properties out of the fundamental frameworks of these rules is challenging but significant and helps in drawing a complete picture of fascinating concepts in chemistry.