The Jellium closed-shell model,a cornerstone of cluster science,has long guided the design of superatoms by dictating electron-counting rules.However,its reliance on precise control of cluster composition and electron...The Jellium closed-shell model,a cornerstone of cluster science,has long guided the design of superatoms by dictating electron-counting rules.However,its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges.Here,we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity(AEA) of aluminum-based clusters,whether with filled or partially filled electron shells,can be dramatically enhanced through the attachment of organic Lewis acid ligands.It was evidenced that the AEA of PAl12can be significantly increased by 2.17 e V after the ligation of two ligands,indicating a remarkable improvement in its electron-accepting ability.This approach yields superhalogen species,offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states,independent of shell occupancy.Remarkably,this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems,hinting at its broader applicability.Given the indispensable role of ligands in cluster synthesis,this strategy holds promise for advancing the field of condensed-phase superatom synthesis,potentially complementing traditional electron-counting rules in a broader range of applications.展开更多
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
基金supported by the National Natural Science Foundation of China (NSFC,Nos.12474274,92161101)the Innovation Project of Jinan Science and Technology Bureau (No.2021GXRC032)the Natural Science Foundation of Shandong Province (No.ZR2024MA091)。
文摘The Jellium closed-shell model,a cornerstone of cluster science,has long guided the design of superatoms by dictating electron-counting rules.However,its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges.Here,we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity(AEA) of aluminum-based clusters,whether with filled or partially filled electron shells,can be dramatically enhanced through the attachment of organic Lewis acid ligands.It was evidenced that the AEA of PAl12can be significantly increased by 2.17 e V after the ligation of two ligands,indicating a remarkable improvement in its electron-accepting ability.This approach yields superhalogen species,offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states,independent of shell occupancy.Remarkably,this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems,hinting at its broader applicability.Given the indispensable role of ligands in cluster synthesis,this strategy holds promise for advancing the field of condensed-phase superatom synthesis,potentially complementing traditional electron-counting rules in a broader range of applications.
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.
