We have synthesized two copper nanoclusters(NCs)with a protection of the same ligand diphenylphosphino-2-pyridine(C_(17)H_(14)NP,dppy for short),formulated as Cu_(4)(dppy)_(4)Cl_(2)and Cu21(dppy)10,respectively.The fo...We have synthesized two copper nanoclusters(NCs)with a protection of the same ligand diphenylphosphino-2-pyridine(C_(17)H_(14)NP,dppy for short),formulated as Cu_(4)(dppy)_(4)Cl_(2)and Cu21(dppy)10,respectively.The former one bears a distorted tetrahedron Cu4 core with its six edges fully protected by chlorine and dppy ligands,while the latter presents a symmetric Cu_(21)core on which ten dppy molecules function as monolayer protection via well-organized monodentate or bidentate coordination.Interestingly,the Cu_(4)(dppy)_(4)Cl_(2)cluster exhibits a strong yellow emission at∼577 nm,while Cu_(21)(dppy)_(10)displays dual emissions in purple(∼368 nm)and green(∼516 nm)regions respectively.In combination with TD-DFT calculations,we demonstrate the origin of altered emissions and unique stability of the two copper nanoclusters pertaining to the ligand coordination and metallic superatomic states.展开更多
In core-shell silver nanoclusters,the control of core structure presents a more formidable challenge compared to that of the shell structure.Here,we report the successful synthesis and characterization of four distinc...In core-shell silver nanoclusters,the control of core structure presents a more formidable challenge compared to that of the shell structure.Here,we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters[MS_(4)@Ag_(12)@Ag_(46)S_(24)(dppb)_(12)](M=Mo or W),each incorporating a cup-like[MS_(4)@Ag_(12)]^(2+)kernel.These nanoclusters were meticulously prepared using(NH_(4))2Mo S4or(NH_(4))_(2)WS_(4)as both a template and a controlled source of S2-ions.Remarkably,we have observed a unique configuration within these eight-electron superatomic Ag_(58) nanoclusters,where the zerovalent Ag atoms reside exclusively within the inner[MS_(4)@Ag_(12)]^(2+)kernel.This stands in contrast to other superatomic clusters possessing an Ag(0)core.Notably,the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C_(2)/c to I 4ˉ.This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane(dppb)ligands,which facilitated enhanced emission through aggregationinduced intermolecular interactions,specifically C-H···πinteractions.Collectively,our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties,shedding light on the crucial roles played by templates and diphosphine ligands in this context.展开更多
α-Keggin polyoxometalates(POMs)[XW_(12)O_(40)]^(n−)(X=Al,Si,P,S)are widely used in batteries owing to their remarkable redox activity.However,the mechanism underlying the applications appears inconsistent with the wi...α-Keggin polyoxometalates(POMs)[XW_(12)O_(40)]^(n−)(X=Al,Si,P,S)are widely used in batteries owing to their remarkable redox activity.However,the mechanism underlying the applications appears inconsistent with the widely accepted covalent bonding nature.Here,first-principles calculations show that XW_(12)are core–shell structures composed of a shell and an XO_(4)^(n−)core,both are stabilized by covalent interactions.Interestingly,owing to the presence of a substantial number of electrons in W_(12)O_(36)shell,the frontier molecular orbitals of XW_(12)are not only strongly delocalized but also exhibit superatomic properties with high-angular momentum electrons that do not conform to the Jellium model.Detailed analysis indicates that energetically high lying filled molecular orbitals(MOs)have reached unusually high-angular momentum characterized by quantum number K or higher,allowing for the accommodation of numerous electrons.This attribute confers strong electron acceptor ability and redox activity to XW_(12).Moreover,electrons added to XW_(12)still occupy the K orbitals and will not cause rearrangement of the MOs,thereby maintaining the stability of these structures.Our findings highlight the structure–activity relationship and provide a direction for tailor-made POMs with specific properties at atomic level.展开更多
5f-elements encaged in a gold superatomic cluster are capable of giving rise to unique optical properties due to their hyperactive valence electrons and great radial components of 5f/6d orbitals. Herein, we review our...5f-elements encaged in a gold superatomic cluster are capable of giving rise to unique optical properties due to their hyperactive valence electrons and great radial components of 5f/6d orbitals. Herein, we review our first-principles studies on electronic structures and spectroscopic properties of a series of actinide-embedded gold superatomic clusters with different dimensions. The three-dimensional（3D） and two-dimensional（2D） superatom clusters possess the 18-electron configuration of 1S21P61D10 and 10-electron configuration of 1S21P41D4, respectively. Importantly, their electronic absorption spectra can also be effectively explained by the superatom orbitals. Specifically, the charge transfer（CT） transitions involved in surface-enhance Raman spectroscopy（SERS） spectra for 3D and 2D structures are both from the filled 1D orbitals, providing the enhancement factors of the order of ～ 10^4 at 488 nm and ～ 10^5 at 456 nm, respectively. This work implies that the superatomic orbital transitions involved in 5f-elements can not only lead to a remarkable spectroscopic performance, but also a new direction for optical design in the future.展开更多
Constructing specific structures from the bottom up with artificial units is an important interdisciplinary topic involving physics,chemistry,materials,and so on.In this work,we theoretically demonstrated the feasibil...Constructing specific structures from the bottom up with artificial units is an important interdisciplinary topic involving physics,chemistry,materials,and so on.In this work,we theoretically demonstrated the feasibility of using superatoms as building blocks to assemble a complex at atomic-level precision.By using a series of actinide-based endohedral metallofullerene(EMF)superatoms that can form one,two,three and four chemical bonds,a planar complex with intra-and inter-molecular interactions was assembled on the Au(111)surface.This complex is composed of two parts,containing ten and eight superatoms,respectively.The electronic structure analysis shows that the electron density inside each part is connected and the closed-shell electronic arrangement system is designed.There is also an obvious van der Waals boundary by physical adsorption between the two parts,and a stable complex is formed.Since this complex is realized by the first-principles calculations of quantum mechanics,our results help not only achieve atomic-level precision construction with artificial superatomic units but also maintain atomic-level functional properties.展开更多
For cluster catalysts,reducing their size to single atoms gives rise to precise and high-selective catalytic performance,at the cost of losing some tunability.Superatoms,the entirety with atom-like electronic shells a...For cluster catalysts,reducing their size to single atoms gives rise to precise and high-selective catalytic performance,at the cost of losing some tunability.Superatoms,the entirety with atom-like electronic shells and fine-tunable properties as clusters,are promising candidates for cluster catalysts.Here,we predicted a superatom-assembled two-dimension Al_(8)O_(3)superatom-oxide framework(SOF) using first principles calculation,where the Al8core comprises two 8-electron Al4superatoms and further linked by oxygen atoms in a graphene-like lattice,resulting in porous and stable geometry.The Al_(8)O_(3)-SOF serves as an efficient superatomic catalyst for nitric oxide(NO) reduction reaction,where the Al4superatomic unit acts cohesively as the active site throughout the catalytic process and its superatomic P orbital plays an important role in activating NO molecule.Additionally,the catalytic activity of Al_(8)O_(3)-SOF increases when the two central Al atoms of the Al8core are replaced by Ga atoms,reducing the limiting potential to -0.48 V comparable to that of the reported Pt(100).Our work proposes a novel series of superatomic catalysts and reveals the superatomic behavior in the catalytic process,providing references for the development of efficient heterogeneous catalysts.展开更多
The manipulation of single atom within the metallic kernel of nanoclusters has attracted considerable attention due to its potentials to elucidate kernel-based structure-property relationships at the single-atom level...The manipulation of single atom within the metallic kernel of nanoclusters has attracted considerable attention due to its potentials to elucidate kernel-based structure-property relationships at the single-atom level.Herein,new-designed chiral bialkynyl ligands,have been chosen as protective agents to isolate two pairs of 8-electron superatomic silver nanoclusters,R/S-Ag39 and R/S-Ag40.X-ray diffraction analysis reveals that Ag39 and Ag40 with the same number of chiral ligands,possess a closely analogous silver skeleton but a single-atomic difference.The incorporation of an extra Ag40th atom into Ag40 evokes two significant changes of structure and property compared to Ag39:(i)a reduction in the symmetry of the entire nanocluster,resulting in an enhancement of kernel-related asymmetry g-factor;(ii)a regulation of the transitions(1P→1D and Ligand(π)→1D)of excited state,leading to a second near-infrared(NIR-II,1000-1700 nm)phosphorescent emission red-shift from 1088 to 1150 nm.This work not only provides vital insights into the relationship between structures and ground/excited states chiroptical activities at the single-atom level,but also presents bialkynyl as a promising stabilizing agent for building superatomic metal nanoclusters.展开更多
Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric...Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallo-fullerene superatoms based on their own bonding properties.Specifically,stable mirror-symmetric sinister and rectus structures are obtained by selecting a super-atom capable of forming four chemical bonds as the chiral center.Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers,which greatly expands the range of chiral spectra com-pared to atom-based molecules.We term this type of chirality based on superatoms as“superatomic-based chirality”.It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.展开更多
Cluster-assembled materials have long been pursued as they can create some unprecedented and desirable properties.Herein,we assemble a class of one-dimensional(1D)ReNX_(4)(X=F,Cl,Br and I)and MFs(M=V,Nb and Ta)nanowir...Cluster-assembled materials have long been pursued as they can create some unprecedented and desirable properties.Herein,we assemble a class of one-dimensional(1D)ReNX_(4)(X=F,Cl,Br and I)and MFs(M=V,Nb and Ta)nanowires by covalently linking their superatomic clusters.These assembled ID nanowires exhibit outstanding energetic and dynamic stabilities,and hold sizable spontaneous polarization,low ferroelectric switching barriers and high critical temperature.Their superior ferroelec-tricity is originated from do-configuration transition metal ions generated by the hybridization of empty d orbitals of metal atoms and p orbitals of non-metal atoms.These critical insights pave a new avenue to fabricate 1D ferroelectrics toward the development of miniaturized and high-density electronic devices using building blocks as cluster with precise structures and functionalities.展开更多
Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,wh...Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,which mainly adjust the shell-filling of clusters,are classical strategies in designing superatoms.Here,by employing the density functional theory(DFT)calculations,we proved that the 1,4-phenylene diisocyanide(CNC_(6)H_(4)NC)ligand could dramatically reduce the adiabatic ionization potentials(AlPs)of the aluminum-based clusters,which have 39,40,and 41 valence electrons,respectively,to give rise to superalkali species without changing their shell-filling.Moreover,the rigid structure of the ligand can be used as a bridge firmly linking the same or different aluminum-based clusters to form superatomic molecules and nanowires.In particular,the bridging process was observed to enhance their nonlinear optical(NLO)responses,which can be further promoted by the oriented external electric field(OEEF).Also,the stable cluster-assembly XAl_(12)(CNC_(6)H_(4)NC)(X=Al,C,and P)nanowires were constructed,which exhibit strong absorption in the visible light region.These findings not only suggest an effective ligand-field strategy in superatom design but also unveil the geometrical and electronic evolution from the CNC_(6)H_(4)NC-based superatoms to superatomic molecules and nanomaterials.展开更多
Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active sites.Here we report a study of Ag_(n)^(+)(n=1-27)clusters reacting with ...Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active sites.Here we report a study of Ag_(n)^(+)(n=1-27)clusters reacting with iodomethane by a flow tube apparatus in tandem with a customized triple quadrupole mass spectrometer.Strong even/odd alternation of the Ag_(n)^(+)is observed in their reactions with CH_(3)I,where silver clusters with even-number,Ag_(2n)^(+),find favorable products of Ag_(2n)I_(1,3)^(+)series,while the Ag_(2n−1)^(+)clusters form Ag_(2n−1)I_(2,4)^(+)products.Interestingly,Ag_(9)^(+)shows up with prominent mass abundance but allows for the formation of Ag_(9)I_(2)^(+),which finds an echo with the formation of Ag_(10)I_(3)^(+).We illustrate the enhanced stability of Ag_(9)I_(2)^(+)and Ag_(10)I_(3)^(+)by showing their significantly enlarged highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)gaps and balanced charge distribution compared with the bare metal clusters,respectively.Also elucidated,is the superatomic nature of these bare and iodinated silver clusters,especially Ag_(9)I_(2)^(+)which mimics the rare-gas compound XeF_(2).This study expands a vivid example of special and general superatoms,and enriches the general knowledge on how a ligand stabilizes a metal cluster.展开更多
Bottom-up constructing all-metal functional materials is challenging,because the metal clusters are prone to lose their original structures during coalensence.In this work,we report that closed-shell coinage metal sup...Bottom-up constructing all-metal functional materials is challenging,because the metal clusters are prone to lose their original structures during coalensence.In this work,we report that closed-shell coinage metal superatoms can achieve direct chemical bonding without losing their electronic properties.The reason is that the supermolecule formed by two superatoms has the same number of bonding and anti-bonding supermolecular orbitals,in which the bonding orbitals contribute to bonding and the antibonding orbitals with anti-phase orbitals delocalized over each monomer to maintain the individual geometric and electronic structural properties.Further analysis indicates the interactions between two superatoms are too weak to break the structure of monomers,which is confirmed by the first-principles molecular dynamics simulations.With these superatoms as the basic units,a series of robust one-dimensional and two-dimensional nanostructures are fabricated.Our findings provide a general strategy to take advantage of superatoms in regulating bonding compared to natural atoms,which paves the way for the bottom-up design of materials with collective properties.展开更多
Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared wi...Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared with that of the isoelectronic entities [Ac@Au14]- and [Pa@Au14]＋ using density functional theory. The calculation results indicate that these clusters all adopt a closed- shell superatomic 18-electron configuration of the 1S21p61D10 Jellium state. The absorption spectrum of Th@Au14 can be interpreted by the Jelliumatic orbital model. In addition, calculated spectra of pyridine-Th@Au14 complexes in the blue laser band exhibit strong peaks attributable to charge transfer （CT） from the metal to the pyridine molecule. These charge-transfer bands lead to a resonant surface-enhanced Raman scattering （SERS） enhancement of -104. This work suggests a basis for designing and synthesizing SERS substrate materials based on actinide-embedded gold superatom models.展开更多
Utilizing a facile top-down synthetic procedure, here we report the finding of a chlorine-passivated Al_(37) superatom cluster. It is demonstrated that the presence of electrophilic groups, severing as protecting liga...Utilizing a facile top-down synthetic procedure, here we report the finding of a chlorine-passivated Al_(37) superatom cluster. It is demonstrated that the presence of electrophilic groups, severing as protecting ligands, alters the valence electron count of the metallic core and stabilize the as-prepared aluminum clusters especially when even-numbered chlorine atoms are located at equilibrium positions. Following the discussion regarding their reasonable stabilities, we illustrate the feasible reaction pathways in forming such chlorine-passivated Al_(37) superatom clusters which bear delocalized superatomic orbitals with five valence 3P^5 electrons shifting to the chlorine ligands indicative of a closed electron shell 2F^(14) of the metal core. The successful synthesis of such chlorine-protected aluminum clusters evidences the compatibility of general theory of cluster chemistry in both gas phase and wet chemistry. Such simple-ligand-protected aluminum clusters exhibit reverse-saturated-absorption(RSA) nonlinear optical property pertaining to electronic transitions within the discrete energy states of cluster materials.展开更多
Assembly is an effective way to realize the functionalization potential of boron-based superatoms. Here we study the interaction between typical boron-based B40 superatoms using the density functional theory. Our resu...Assembly is an effective way to realize the functionalization potential of boron-based superatoms. Here we study the interaction between typical boron-based B40 superatoms using the density functional theory. Our results reveal that different oligomers constructed by modulating the arrangement of two B40 superatoms still retain some of the superatomic properties associated with their monomeric form despite possessing different electronic structures. While the inner shell superatomic orbitals maintain their electronic localization, the valence shell superatomic orbitals cannot maintain their original shape due to bonding and antibonding hybridization. Furthermore, the decreasing of band gap means that the B40 oligomers could achieve a transformation from insulators to semiconductors. The decreased band gap is possibly due to the disappearance of the superatomic orbitals with the principal quantum number of two. Our findings highlight that superatom–superatom interactions could induce synergy effects that differ from their monomers. Therefore, this research will aid in the development of new materials and devices that are constructed from superatoms.展开更多
Understanding the stability and reactivity of silver clusters toward oxygen provides insights to design new materials of coinage metals with atomic precision.Herein,we report a systematic study on anionic silver clust...Understanding the stability and reactivity of silver clusters toward oxygen provides insights to design new materials of coinage metals with atomic precision.Herein,we report a systematic study on anionic silver clusters,Ag_(n)^(−)(n=10-34),by reacting them with O_(2) under multiple-collision conditions.Mass spectrometry observation presents the odd-even alternation effect on the reaction rates of these Agn−clusters.展开更多
Boron allotropes are known to be predominately constructed by icosahedral B_(12) cages,while icosahedral-B_(12) stuffing proves to effectively improve the stability of fullerene-like boron nanoclusters in the size ran...Boron allotropes are known to be predominately constructed by icosahedral B_(12) cages,while icosahedral-B_(12) stuffing proves to effectively improve the stability of fullerene-like boron nanoclusters in the size range between B_(98)–B_(102).However,the thermodynamically most stable core-shell borospherenes with a B_(12) icosahedron at the center still remains unknown.Based on the structural motif of D5h C_(70) and extensive first-principles theory calculations,we predict herein the high-symmetry C5v B111+(3)which satisfies the Wade’s n+1 and n+2 skeletal electron counting rules exactly and the approximately electron sufficient Cs B_(111)(4),Cs B_(112)(5),Cs B_(113)(6),and Cs B_(114)(7)which are the most stable neutral core-shell borospherenes with a B_(12) icosahedron at the center reported to date in the size range between B_(68)–B_(130),with Cs B112(5)being the thermodynamically most favorite species in the series.Detailed orbital and bonding analyses indicate that these spherically aromatic species all contain a negatively charged icosahedral B_(122)−core at the center which exhibits typical superatomic behaviors in the electronic configuration of 1S21P61D101F8,with its dangling valences saturated by twelve radial B-B 2c-2eσbonds between the B_(12) inner core and the B_(70) outer shell.The infrared(IR)and Raman spectra of the concerned species are computationally simulated to facilitate their future characterizations.展开更多
基金the National Natural Science Foundation of China(Nos.22003072 and 21722308),the Ministry of Science and Technology of the People’s Republic of China(No. 2020YFA0714602).
文摘We have synthesized two copper nanoclusters(NCs)with a protection of the same ligand diphenylphosphino-2-pyridine(C_(17)H_(14)NP,dppy for short),formulated as Cu_(4)(dppy)_(4)Cl_(2)and Cu21(dppy)10,respectively.The former one bears a distorted tetrahedron Cu4 core with its six edges fully protected by chlorine and dppy ligands,while the latter presents a symmetric Cu_(21)core on which ten dppy molecules function as monolayer protection via well-organized monodentate or bidentate coordination.Interestingly,the Cu_(4)(dppy)_(4)Cl_(2)cluster exhibits a strong yellow emission at∼577 nm,while Cu_(21)(dppy)_(10)displays dual emissions in purple(∼368 nm)and green(∼516 nm)regions respectively.In combination with TD-DFT calculations,we demonstrate the origin of altered emissions and unique stability of the two copper nanoclusters pertaining to the ligand coordination and metallic superatomic states.
基金financial support from the National Natural Science Foundation of China(Nos.21771071,22171094,21925104,and 92261204)the Hubei Provincial Natural Science Foundation of China(No.2021CFA020)。
文摘In core-shell silver nanoclusters,the control of core structure presents a more formidable challenge compared to that of the shell structure.Here,we report the successful synthesis and characterization of four distinct silver thiolate nanoclusters[MS_(4)@Ag_(12)@Ag_(46)S_(24)(dppb)_(12)](M=Mo or W),each incorporating a cup-like[MS_(4)@Ag_(12)]^(2+)kernel.These nanoclusters were meticulously prepared using(NH_(4))2Mo S4or(NH_(4))_(2)WS_(4)as both a template and a controlled source of S2-ions.Remarkably,we have observed a unique configuration within these eight-electron superatomic Ag_(58) nanoclusters,where the zerovalent Ag atoms reside exclusively within the inner[MS_(4)@Ag_(12)]^(2+)kernel.This stands in contrast to other superatomic clusters possessing an Ag(0)core.Notably,the introduction of phenyl-containing compounds during the synthesis process induced a transformation in the space group symmetry from C_(2)/c to I 4ˉ.This transformative effect was found to originate from the interplay between adjacent 1,4-bis(diphenylphosphino)butane(dppb)ligands,which facilitated enhanced emission through aggregationinduced intermolecular interactions,specifically C-H···πinteractions.Collectively,our findings contribute substantively to the understanding of the intricate relationship between nanocluster structures and their corresponding properties,shedding light on the crucial roles played by templates and diphosphine ligands in this context.
基金supported by the National Natural Science Foundation of China(under grant numbers 12174272 and 11974136)。
文摘α-Keggin polyoxometalates(POMs)[XW_(12)O_(40)]^(n−)(X=Al,Si,P,S)are widely used in batteries owing to their remarkable redox activity.However,the mechanism underlying the applications appears inconsistent with the widely accepted covalent bonding nature.Here,first-principles calculations show that XW_(12)are core–shell structures composed of a shell and an XO_(4)^(n−)core,both are stabilized by covalent interactions.Interestingly,owing to the presence of a substantial number of electrons in W_(12)O_(36)shell,the frontier molecular orbitals of XW_(12)are not only strongly delocalized but also exhibit superatomic properties with high-angular momentum electrons that do not conform to the Jellium model.Detailed analysis indicates that energetically high lying filled molecular orbitals(MOs)have reached unusually high-angular momentum characterized by quantum number K or higher,allowing for the accommodation of numerous electrons.This attribute confers strong electron acceptor ability and redox activity to XW_(12).Moreover,electrons added to XW_(12)still occupy the K orbitals and will not cause rearrangement of the MOs,thereby maintaining the stability of these structures.Our findings highlight the structure–activity relationship and provide a direction for tailor-made POMs with specific properties at atomic level.
基金supported by the National Natural Science Foundation of China(Grant No.11374004)the Science and Technology Development Program of Jilin Province,China(Grant No.20150519021JH)+1 种基金the Fok Ying Tung Education Foundation,China(Grant No.142001)the Support from the High Performance Computing Center(HPCC)of Jilin University,China
文摘5f-elements encaged in a gold superatomic cluster are capable of giving rise to unique optical properties due to their hyperactive valence electrons and great radial components of 5f/6d orbitals. Herein, we review our first-principles studies on electronic structures and spectroscopic properties of a series of actinide-embedded gold superatomic clusters with different dimensions. The three-dimensional（3D） and two-dimensional（2D） superatom clusters possess the 18-electron configuration of 1S21P61D10 and 10-electron configuration of 1S21P41D4, respectively. Importantly, their electronic absorption spectra can also be effectively explained by the superatom orbitals. Specifically, the charge transfer（CT） transitions involved in surface-enhance Raman spectroscopy（SERS） spectra for 3D and 2D structures are both from the filled 1D orbitals, providing the enhancement factors of the order of ～ 10^4 at 488 nm and ～ 10^5 at 456 nm, respectively. This work implies that the superatomic orbital transitions involved in 5f-elements can not only lead to a remarkable spectroscopic performance, but also a new direction for optical design in the future.
基金supported by the National Natural Science Foundation of China(Grant Nos.11974136,11674123,and 11374004)
文摘Constructing specific structures from the bottom up with artificial units is an important interdisciplinary topic involving physics,chemistry,materials,and so on.In this work,we theoretically demonstrated the feasibility of using superatoms as building blocks to assemble a complex at atomic-level precision.By using a series of actinide-based endohedral metallofullerene(EMF)superatoms that can form one,two,three and four chemical bonds,a planar complex with intra-and inter-molecular interactions was assembled on the Au(111)surface.This complex is composed of two parts,containing ten and eight superatoms,respectively.The electronic structure analysis shows that the electron density inside each part is connected and the closed-shell electronic arrangement system is designed.There is also an obvious van der Waals boundary by physical adsorption between the two parts,and a stable complex is formed.Since this complex is realized by the first-principles calculations of quantum mechanics,our results help not only achieve atomic-level precision construction with artificial superatomic units but also maintain atomic-level functional properties.
基金the National Key Basic Research Program，the National Natural Science Foundation of China，the Chinese Academy of Sciences，USTCSCC, SCCAS, Tianjin, and Shanghai Supercomputer Centers
基金supported by the National Natural Science Foundation of China (22103001, U21A20317)the Natural Science Foundation of Anhui Province (2108085QB64)the Fundamental Research Funds for the Central Universities (20720220009)。
文摘For cluster catalysts,reducing their size to single atoms gives rise to precise and high-selective catalytic performance,at the cost of losing some tunability.Superatoms,the entirety with atom-like electronic shells and fine-tunable properties as clusters,are promising candidates for cluster catalysts.Here,we predicted a superatom-assembled two-dimension Al_(8)O_(3)superatom-oxide framework(SOF) using first principles calculation,where the Al8core comprises two 8-electron Al4superatoms and further linked by oxygen atoms in a graphene-like lattice,resulting in porous and stable geometry.The Al_(8)O_(3)-SOF serves as an efficient superatomic catalyst for nitric oxide(NO) reduction reaction,where the Al4superatomic unit acts cohesively as the active site throughout the catalytic process and its superatomic P orbital plays an important role in activating NO molecule.Additionally,the catalytic activity of Al_(8)O_(3)-SOF increases when the two central Al atoms of the Al8core are replaced by Ga atoms,reducing the limiting potential to -0.48 V comparable to that of the reported Pt(100).Our work proposes a novel series of superatomic catalysts and reveals the superatomic behavior in the catalytic process,providing references for the development of efficient heterogeneous catalysts.
基金supported by the National Natural Science Foundation of China(92361301,22325105,22201159,22171164,and 52261135637)the Instrument Improvement Funds of Shandong University Public Technology Platform(ts20220102).
文摘The manipulation of single atom within the metallic kernel of nanoclusters has attracted considerable attention due to its potentials to elucidate kernel-based structure-property relationships at the single-atom level.Herein,new-designed chiral bialkynyl ligands,have been chosen as protective agents to isolate two pairs of 8-electron superatomic silver nanoclusters,R/S-Ag39 and R/S-Ag40.X-ray diffraction analysis reveals that Ag39 and Ag40 with the same number of chiral ligands,possess a closely analogous silver skeleton but a single-atomic difference.The incorporation of an extra Ag40th atom into Ag40 evokes two significant changes of structure and property compared to Ag39:(i)a reduction in the symmetry of the entire nanocluster,resulting in an enhancement of kernel-related asymmetry g-factor;(ii)a regulation of the transitions(1P→1D and Ligand(π)→1D)of excited state,leading to a second near-infrared(NIR-II,1000-1700 nm)phosphorescent emission red-shift from 1088 to 1150 nm.This work not only provides vital insights into the relationship between structures and ground/excited states chiroptical activities at the single-atom level,but also presents bialkynyl as a promising stabilizing agent for building superatomic metal nanoclusters.
基金National Natural Science Foundation of China,Grant/Award Numbers:11974136,12174272。
文摘Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallo-fullerene superatoms based on their own bonding properties.Specifically,stable mirror-symmetric sinister and rectus structures are obtained by selecting a super-atom capable of forming four chemical bonds as the chiral center.Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers,which greatly expands the range of chiral spectra com-pared to atom-based molecules.We term this type of chirality based on superatoms as“superatomic-based chirality”.It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.
基金supported by the National Natural Science Foundation of China(Nos.12004065,91961204,12222403,and 11974068)the Doctoral Start-up Foundation of Liaoning Province(No.2022-BS-081)the Fundamental Research Funds for the Central Univeristies(No.DUT24LAB114).
文摘Cluster-assembled materials have long been pursued as they can create some unprecedented and desirable properties.Herein,we assemble a class of one-dimensional(1D)ReNX_(4)(X=F,Cl,Br and I)and MFs(M=V,Nb and Ta)nanowires by covalently linking their superatomic clusters.These assembled ID nanowires exhibit outstanding energetic and dynamic stabilities,and hold sizable spontaneous polarization,low ferroelectric switching barriers and high critical temperature.Their superior ferroelec-tricity is originated from do-configuration transition metal ions generated by the hybridization of empty d orbitals of metal atoms and p orbitals of non-metal atoms.These critical insights pave a new avenue to fabricate 1D ferroelectrics toward the development of miniaturized and high-density electronic devices using building blocks as cluster with precise structures and functionalities.
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)+3 种基金the Natural Science Foundation of Jiangsu Province(No.BK20170396)the Natural Science Foundation of Shandong Province(No.ZR2020ZD35)the Young Scholars Program of Shandong University(YSPSDU)(No.2018WLJH48)the Qilu Youth Scholar Funding of Shandong University.
文摘Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,which mainly adjust the shell-filling of clusters,are classical strategies in designing superatoms.Here,by employing the density functional theory(DFT)calculations,we proved that the 1,4-phenylene diisocyanide(CNC_(6)H_(4)NC)ligand could dramatically reduce the adiabatic ionization potentials(AlPs)of the aluminum-based clusters,which have 39,40,and 41 valence electrons,respectively,to give rise to superalkali species without changing their shell-filling.Moreover,the rigid structure of the ligand can be used as a bridge firmly linking the same or different aluminum-based clusters to form superatomic molecules and nanowires.In particular,the bridging process was observed to enhance their nonlinear optical(NLO)responses,which can be further promoted by the oriented external electric field(OEEF).Also,the stable cluster-assembly XAl_(12)(CNC_(6)H_(4)NC)(X=Al,C,and P)nanowires were constructed,which exhibit strong absorption in the visible light region.These findings not only suggest an effective ligand-field strategy in superatom design but also unveil the geometrical and electronic evolution from the CNC_(6)H_(4)NC-based superatoms to superatomic molecules and nanomaterials.
基金supported by the Ministry of Science and Technology of China(2020YFA0714602)the National Natural Science Foundation of China(21722308,22003072)CAS Instrument Development Project(Y5294512C1)。
文摘Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active sites.Here we report a study of Ag_(n)^(+)(n=1-27)clusters reacting with iodomethane by a flow tube apparatus in tandem with a customized triple quadrupole mass spectrometer.Strong even/odd alternation of the Ag_(n)^(+)is observed in their reactions with CH_(3)I,where silver clusters with even-number,Ag_(2n)^(+),find favorable products of Ag_(2n)I_(1,3)^(+)series,while the Ag_(2n−1)^(+)clusters form Ag_(2n−1)I_(2,4)^(+)products.Interestingly,Ag_(9)^(+)shows up with prominent mass abundance but allows for the formation of Ag_(9)I_(2)^(+),which finds an echo with the formation of Ag_(10)I_(3)^(+).We illustrate the enhanced stability of Ag_(9)I_(2)^(+)and Ag_(10)I_(3)^(+)by showing their significantly enlarged highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)gaps and balanced charge distribution compared with the bare metal clusters,respectively.Also elucidated,is the superatomic nature of these bare and iodinated silver clusters,especially Ag_(9)I_(2)^(+)which mimics the rare-gas compound XeF_(2).This study expands a vivid example of special and general superatoms,and enriches the general knowledge on how a ligand stabilizes a metal cluster.
基金the National Science Foundation of China(Nos.11974136 and 11674123).
文摘Bottom-up constructing all-metal functional materials is challenging,because the metal clusters are prone to lose their original structures during coalensence.In this work,we report that closed-shell coinage metal superatoms can achieve direct chemical bonding without losing their electronic properties.The reason is that the supermolecule formed by two superatoms has the same number of bonding and anti-bonding supermolecular orbitals,in which the bonding orbitals contribute to bonding and the antibonding orbitals with anti-phase orbitals delocalized over each monomer to maintain the individual geometric and electronic structural properties.Further analysis indicates the interactions between two superatoms are too weak to break the structure of monomers,which is confirmed by the first-principles molecular dynamics simulations.With these superatoms as the basic units,a series of robust one-dimensional and two-dimensional nanostructures are fabricated.Our findings provide a general strategy to take advantage of superatoms in regulating bonding compared to natural atoms,which paves the way for the bottom-up design of materials with collective properties.
基金Acknowledgements We would like to thank Drs. Jun Liu and Lei Chen for the stimulating discussions. We would also like to acknowledge the support of the National Natural Science Foundation of China （No. 11374004） and the Science and Technology Development Program of Jilin Province of China （No. 20150519021JH）. Z. W. also acknowledges the Fok Ying Tung Education Foundation （No. 142001） and High Performance Computing Center of Jilin University.
文摘Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared with that of the isoelectronic entities [Ac@Au14]- and [Pa@Au14]＋ using density functional theory. The calculation results indicate that these clusters all adopt a closed- shell superatomic 18-electron configuration of the 1S21p61D10 Jellium state. The absorption spectrum of Th@Au14 can be interpreted by the Jelliumatic orbital model. In addition, calculated spectra of pyridine-Th@Au14 complexes in the blue laser band exhibit strong peaks attributable to charge transfer （CT） from the metal to the pyridine molecule. These charge-transfer bands lead to a resonant surface-enhanced Raman scattering （SERS） enhancement of -104. This work suggests a basis for designing and synthesizing SERS substrate materials based on actinide-embedded gold superatom models.
基金supported by the Key Research Program of Frontier Sciences (QYZDB-SSW-SLH024)the National Natural Science Foundation of China (21722308)the National Thousand Youth Talents Program
文摘Utilizing a facile top-down synthetic procedure, here we report the finding of a chlorine-passivated Al_(37) superatom cluster. It is demonstrated that the presence of electrophilic groups, severing as protecting ligands, alters the valence electron count of the metallic core and stabilize the as-prepared aluminum clusters especially when even-numbered chlorine atoms are located at equilibrium positions. Following the discussion regarding their reasonable stabilities, we illustrate the feasible reaction pathways in forming such chlorine-passivated Al_(37) superatom clusters which bear delocalized superatomic orbitals with five valence 3P^5 electrons shifting to the chlorine ligands indicative of a closed electron shell 2F^(14) of the metal core. The successful synthesis of such chlorine-protected aluminum clusters evidences the compatibility of general theory of cluster chemistry in both gas phase and wet chemistry. Such simple-ligand-protected aluminum clusters exhibit reverse-saturated-absorption(RSA) nonlinear optical property pertaining to electronic transitions within the discrete energy states of cluster materials.
基金supported by the National Natural Science Foundation of China (11674123 and 11374004)
文摘Assembly is an effective way to realize the functionalization potential of boron-based superatoms. Here we study the interaction between typical boron-based B40 superatoms using the density functional theory. Our results reveal that different oligomers constructed by modulating the arrangement of two B40 superatoms still retain some of the superatomic properties associated with their monomeric form despite possessing different electronic structures. While the inner shell superatomic orbitals maintain their electronic localization, the valence shell superatomic orbitals cannot maintain their original shape due to bonding and antibonding hybridization. Furthermore, the decreasing of band gap means that the B40 oligomers could achieve a transformation from insulators to semiconductors. The decreased band gap is possibly due to the disappearance of the superatomic orbitals with the principal quantum number of two. Our findings highlight that superatom–superatom interactions could induce synergy effects that differ from their monomers. Therefore, this research will aid in the development of new materials and devices that are constructed from superatoms.
基金support for this work was provided by the National Natural Science Foundation of China(nos.21802146,21722308,11974068,and 91961204)the CAS Key Research Project of Frontier Science(CAS grant no.QYZDB-SSW-SLH024).
文摘Understanding the stability and reactivity of silver clusters toward oxygen provides insights to design new materials of coinage metals with atomic precision.Herein,we report a systematic study on anionic silver clusters,Ag_(n)^(−)(n=10-34),by reacting them with O_(2) under multiple-collision conditions.Mass spectrometry observation presents the odd-even alternation effect on the reaction rates of these Agn−clusters.
基金This work was supported by the National Natural Science Foundation of China(Nos.21720102006 and 21973057 to S.-D.Li and 21473106 to H.-G.Lu).
文摘Boron allotropes are known to be predominately constructed by icosahedral B_(12) cages,while icosahedral-B_(12) stuffing proves to effectively improve the stability of fullerene-like boron nanoclusters in the size range between B_(98)–B_(102).However,the thermodynamically most stable core-shell borospherenes with a B_(12) icosahedron at the center still remains unknown.Based on the structural motif of D5h C_(70) and extensive first-principles theory calculations,we predict herein the high-symmetry C5v B111+(3)which satisfies the Wade’s n+1 and n+2 skeletal electron counting rules exactly and the approximately electron sufficient Cs B_(111)(4),Cs B_(112)(5),Cs B_(113)(6),and Cs B_(114)(7)which are the most stable neutral core-shell borospherenes with a B_(12) icosahedron at the center reported to date in the size range between B_(68)–B_(130),with Cs B112(5)being the thermodynamically most favorite species in the series.Detailed orbital and bonding analyses indicate that these spherically aromatic species all contain a negatively charged icosahedral B_(122)−core at the center which exhibits typical superatomic behaviors in the electronic configuration of 1S21P61D101F8,with its dangling valences saturated by twelve radial B-B 2c-2eσbonds between the B_(12) inner core and the B_(70) outer shell.The infrared(IR)and Raman spectra of the concerned species are computationally simulated to facilitate their future characterizations.
