Density functional theory calculations have been performed to study the interaction of small silver clusters, Ag2-Ag9, with HCN. The adsorption of HCN on-top site of the silver cluster, among various possible sites, i...Density functional theory calculations have been performed to study the interaction of small silver clusters, Ag2-Ag9, with HCN. The adsorption of HCN on-top site of the silver cluster, among various possible sites, is energetically preferred. The adsorption energies of HCN on the silver clusters reach a local maximum at n = 4, which is only about 0.450 eV, indicating that the adsorbed HCN molecule is weakly perturbed. The adsorbed C-N and C-H stretching frequencies are blue- and red-shifted compared with the values of free HCN, respectively.展开更多
The interactions between AgnO- （n=1-8） and H2 （or D2） were explored by combination of the mass spectroscopy experiments and density function theory （DFT） calculations. The experiments found that all oxygen atoms...The interactions between AgnO- （n=1-8） and H2 （or D2） were explored by combination of the mass spectroscopy experiments and density function theory （DFT） calculations. The experiments found that all oxygen atoms in AgnO- （n--1-8） are inert in the interactions with H2 or D2 at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation （PROX） of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between AgnO- （n=1-8） and H2 were explored using DFT calculations. The results indicated that adsorption of H2 on any site of AgnO- （n=1-8） is extremely weak, and oxidation of H2 by any kind of oxygen in AgnO- （n=1-8） has an apparent barrier strongly dependent on the adsorption style of the ＂O＂. These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.展开更多
New types of fluorescence DNA-based silver nanoclusters（DNAn-Ag NCs, n = 1, 2, 3c, 4c, 5c） were synthesized by C3T-rich nucleotides as templates. It is found that the assembly of DNAn-Ag NCs with nucleotides contain...New types of fluorescence DNA-based silver nanoclusters（DNAn-Ag NCs, n = 1, 2, 3c, 4c, 5c） were synthesized by C3T-rich nucleotides as templates. It is found that the assembly of DNAn-Ag NCs with nucleotides containing GAG sequences produce silver clusters with an enhanced red emission. Results indicate that GAG is the good enhancer of DNAn-Ag NCs constructed by C3T-rich nucleotides. The fluorescence titration reveals that enhanced red emission is sensitive to Fe（Ⅲ/Ⅱ） ions with the formation of non-emission nanoclusters. Thus, the GAG-containing nucleotide can be an enhancer for the emission of silver clusters with C3T-rich nucleotide and a mediator of the iron-cluster interplay.展开更多
At the Douglas-Kroll-Hess （DKI4） level, the B3PW91 functional along with the all-eleclron relativistic basis sets of valence triple and quadruple zeta qualities are used to determine the structure, stability, and el...At the Douglas-Kroll-Hess （DKI4） level, the B3PW91 functional along with the all-eleclron relativistic basis sets of valence triple and quadruple zeta qualities are used to determine the structure, stability, and electronic properties of the small silver clusters （Agn, n ≤ 7）. The results presented in this study are in good agreement with the experimental data and theoretical values obtained at a higher level of theory from the literature. Static polarizability and hyperpolarizability are also reported. It is verified that the mean dipole polarizability per atom exhibits an odd-even oscillation and that the polarizability anisotropy is directly related to the cluster shape. In this article, the first study of hyperpolarizabilities of small silver clusters is presented. Except for the monomer, the second hyperpolarizabilities of the silver clusters are significantly larger than those of the copper clusters.展开更多
Fruitful efforts have been made for the assembly of nanosized silver clusters,and the majority of which are protected by thiolates and alkynyl ligands.By comparison,the reported silver clusters or silvercluster-based ...Fruitful efforts have been made for the assembly of nanosized silver clusters,and the majority of which are protected by thiolates and alkynyl ligands.By comparison,the reported silver clusters or silvercluster-based supramolecular networks protected by N-donor ligands are very rare because of the hard basicity of N-donor ligands with respect to the soft acid Ag(Ⅰ).Here,by using an N-donor ligand,a 2D Cl@Ag_(11)N_(24)-based supramolecular network[Cl@Ag_(11)(L)_(8)X_(2)]_(n)(X=CF_(3)COO^(-)for 1,NO_(3)^(-)for 2 and CF_(3)SO_(3)^(-)for 3)has been constructed with a Ag-O bond as the linker.This high-nuclearity silver cluster Cl@Ag_(11)N_(24) has an open dendritic structure with a high coordination ratio of the N atom,which is different from the well-established macrocycle,spheroidal cage and core-shell architectures based on silver-thiolate/alkynyl/phosphine clusters.The stability and assembly process of the 2D network has been studied by high-resolution electrospray mass spectrometry(HR-ESI-MS).Notably,1 shows an intriguing dual-emission feature that is strongly influenced by different excitation wavelengths and temperatures.Significantly,this work sheds new light on the construction of novel silver clusters and supramolecular networks based on them and provides a kind of luminescent material.展开更多
Metal clusters with circularly polarized luminescent(CPL)activity have potential applications in security encoding,encrypted transmission,information stor-age,and so on.However,constructing CPL-active metal clusters o...Metal clusters with circularly polarized luminescent(CPL)activity have potential applications in security encoding,encrypted transmission,information stor-age,and so on.However,constructing CPL-active metal clusters on a large scale using self-assembly-based synthetic approaches has been challenging.Herein,we present a collaborative strategy to assem-ble a chiral cyclic hydrogen-bonding(HB)platform(γ-cyclodextrin(γ-CD))onto a photoluminescent sil-ver cluster to form a supramolecular adduct(Ag_(6)@γ-CD).The Ag6@γ-CD fully leverages the advantages of its individual components and exhibits notable CPL activity.Single-crystal X-ray diffraction and sys-tematic photoluminescence investigation reveal that the cyclic HB motif formed between Ag_(6)andγ-CD effectively promotes the population of the first ex-cited state(S 1)and facilitates supramolecular chiral transfer fromγ-CD to Ag_(6),resulting in the boosted CPL lighting.Furthermore,the decagram-scale synthesis of a functionalized adduct has been accomplished using mechanochemistry techniques,providing a material guarantee for the practical applications.展开更多
Aggregation-induced emission(AIE)and thermally activated delayed fluorescence(TADF)are two optoelectronic properties with great potential for applications.However,metal nanoclusters exhibiting both AIE and TADF charac...Aggregation-induced emission(AIE)and thermally activated delayed fluorescence(TADF)are two optoelectronic properties with great potential for applications.However,metal nanoclusters exhibiting both AIE and TADF characteristics have not been extensively studied.This study investigates a binary cocrystal system based on silver nanoclusters—Ag_(6)(Et_(2)NCS_(2))6·[Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6]_(2)(1-Ag_(6)·(Ag_(11))_(2)),aiming to explore the synergistic effects between flexible-alkyl dithiol and rigid monothiol ligands.Due to the introduction of Ag_(6)structures,the system exhibits enhanced stability and modulated optical properties.The binary tricluster 1-Ag_(6)·(Ag_(11))_(2)demonstrates significant AIE behavior,with an approximately 15-fold increase in intensity when the water volume fraction(fw)is 60%.Single-crystal X-ray diffraction analysis indicates that the enhanced AIE effect originates from intercluster hydrogen bonding interactions,which drive the self-assembly of sub-clusters and form hierarchical structures,thereby suppressing ligand rotation.In addition,the system exhibits the TADF phenomenon in the temperature range of 100−175 K.In order to further investigate the effect of ligand variations on optical properties,two unitary clusters,Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6(2-Ag_(11)-AS)and Ag_(11)(tBuS)_(3)(Et_(2)NCS_(2))6(3-Ag_(11)-BS),are synthesized,and their roles in regulating optoelectronic properties are explored through ligand exchange reactions.This study provides important insights for the development of efficient luminescent materials with AIE and TADF properties,highlighting the critical roles of ligand exchange and structural configuration.展开更多
Comparing to the conventional polyoxometalate(POM)-templated silver(Ag)clusters,asymmetrically covered POM-templated Ag clusters have been rarely reported.In this work,a new Ag cluster,H[Co(SiW_(11)O_(39))Co_(4)(OH)_(...Comparing to the conventional polyoxometalate(POM)-templated silver(Ag)clusters,asymmetrically covered POM-templated Ag clusters have been rarely reported.In this work,a new Ag cluster,H[Co(SiW_(11)O_(39))Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))@Ag_(37)(^(t)BuC≡C)_(23)(NO_(3))_(2)(DMF)_(3)](Ag_(37)Co_(5)),has been successfully prepared using a facile solvothermal approach.Such a unique asymmetrical architecture is ascribed to the uneven charge distribution of the in situ generated[Co(SiW_(11)O_(39))]^(6-)and[Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))]^(7-)moieties,leading to the asymmetrical coverage of alkynyl-protected Ag shell.Various physicochemical and catalytic studies revealed that the resulting solid-state Ag_(37)Co_(5) crystals exhibited interesting temperature-dependent photoluminescence property,efficient and recyclable photothermal conversion ability,and good catalytic activity towards the detoxication of 4-nitrophenol.展开更多
Establishing the correlation between inter-cluster assembly and auxiliary ligands at the atomic level is crucial for the development of metal cluster science.In this work,we report the successful preparation and chara...Establishing the correlation between inter-cluster assembly and auxiliary ligands at the atomic level is crucial for the development of metal cluster science.In this work,we report the successful preparation and characterization of three Ag clusters,discrete 0-D Ag_(51)S_(6)Cl_(3)(i PrS)_(21)(TsO)_(15)CH_(3)CN(0-D Ag_(51),i PrS–=isopropanethiolate,TsO–=toluenesulfonate),1-D{Ag_(38)S_(4)-(i PrS)_(18)(PhCOO)_(12)}n(1-D Ag_(38),PHCOO–=benzoate),and 2-D{Ag_(2)0(SO_(4))Cl_(2)(i PrS)10(NO_(3))6}n(2-D Ag_(20)),using a delicate auxiliary-ligand-induced strategy.Structural analyses reveal that the types of auxiliary ligands can readily affect the structure and dimensionality of resulting Ag clusters.The addition of different surface auxiliary ligands from TsO–to PhCOO–and then to NO_(3)–leads to the formation of 0-D Ag_(51) to 1-D Ag_(38) and then to 2-D Ag_(2)0 clusters under otherwise identical reaction conditions,respectively.The resulting Ag clusters exhibited structure-related optical/luminescence properties and distinct bathochromic shifts as revealed by the temperature-dependent luminescence and single-crystal X-ray diffraction studies.展开更多
The development of stimuli-responsive circularly polarized luminescence(CPL)materials is quite attractive but challenging.Here,a pair of atomically precise enan-tiomers R/S-Ag20 nanoclusters has been synthesized using...The development of stimuli-responsive circularly polarized luminescence(CPL)materials is quite attractive but challenging.Here,a pair of atomically precise enan-tiomers R/S-Ag20 nanoclusters has been synthesized using chiral acid ligands.And then,stimuli-responsive CPL materials were developed by assembling the chiral silver nanoclusters with an achiral bridging ligand.The atomically precise silver cluster-assembled materials produce CPL with a dissymmetry factor(|glum|)of 1×10-3,through the high-efficiency chiral induction process.More interestingly,the single CPL band at room temperature could quickly transform into highly separated dual CPL emissions at low temperature.This study provides a new strategy for the rational functionalization of chiral silver clusters in preparing cluster-based CPL emitters and enriches the types of stimuli-responsive CPL materials.展开更多
In this work,three stable dumbbell-shaped silver clusters 1~3,formed by a novel bifunctional ligand Ph2P-C6H4-3-C=CH,are presented.All three complexes have cage structures constructed with thirty-six silver atoms,whic...In this work,three stable dumbbell-shaped silver clusters 1~3,formed by a novel bifunctional ligand Ph2P-C6H4-3-C=CH,are presented.All three complexes have cage structures constructed with thirty-six silver atoms,which are templated by chloride anions.During the self-assembly process of silver acetylides,argentophilic interactions and Ag(I)-ethynide interactions are important for the formation of silver cores to yield a diversity of silver clusters.Weak molecular interactions(π-π,C-H…π,C-H…F,C-H…O)are also found in these complexes,which are crucial to stabilizing these silver clusters.Compared with simple alkynyl ligands(RC≡C-),the introduction of phosphine groups into alkynyl ligand can effectively control the undesired infinite growth of silver acetylides.The photophysical behaviors of complexes 1~3 are studied,showing intense orange roomtemperature luminescence in the solid state upon the exposure to UV light.The luminescence mainly arises from ligand-to-metal charge transfer(LMCT)and metal-cluster-centered transitions(MC)within the silver clusters.展开更多
A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence ...A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.展开更多
A tetrahedral silver(I) cluster complex {Ag4[HC(PPh2)3](S2PPh2)3}ClO4(1,HC(PPh2)3 = 1,1,1-tris(triphenylphosphino)methane, S2PPh2 = diphenyldithiophosphinate) was synthesized by assembling silver ion with phosphor and...A tetrahedral silver(I) cluster complex {Ag4[HC(PPh2)3](S2PPh2)3}ClO4(1,HC(PPh2)3 = 1,1,1-tris(triphenylphosphino)methane, S2PPh2 = diphenyldithiophosphinate) was synthesized by assembling silver ion with phosphor and sulphur mixed-ligand system. The complex was characterized by single-crystal X-ray crystallography, high-resolution mass spectroscopy and thermal analysis. In the crystal structure, an inverted tetrahedron was constructed from Ag4 metal skeleton. The Ag4 cage was stabilized by three diphenyldithiophosphinate ligands and one 1,1,1-tris(triphenylphosphino)methane ligand. 1 exhibits luminescent properties in solid state. A bright yellow-green emission centered at 533 nm has been observed in solid state. Large Stokes' shifts with long range of emissive lifetime indicate that the emission likely originates from a triplet state parentage.展开更多
A new 1D silver cluster-assembled complex Ag_(10)bpy-CH_3CN exhibiting intense photoluminescence was reported. Upon the loss of coordinated acetonitrile, Ag_(10)bpy-CH_3CN form Ag_(10)bpy with Ag_(10)S_6 cores slightl...A new 1D silver cluster-assembled complex Ag_(10)bpy-CH_3CN exhibiting intense photoluminescence was reported. Upon the loss of coordinated acetonitrile, Ag_(10)bpy-CH_3CN form Ag_(10)bpy with Ag_(10)S_6 cores slightly distorted, being accompanied with photoluminescence quenching. Inverse process can be realized by treating Ag_(10)bpy with acetonitrile and shows a selectively erasable photoluminescent switch.展开更多
Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-inv...Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.展开更多
Resistive switching Ag/Ag2S nanoclusters were formed by sulphidation of melting-dispersed thin and continuous Ag films. The morphology, structure and electrical properties of the prepared clusters were characterized b...Resistive switching Ag/Ag2S nanoclusters were formed by sulphidation of melting-dispersed thin and continuous Ag films. The morphology, structure and electrical properties of the prepared clusters were characterized by scanning (SEM), transmitting electron (TEM), scanning resistance microscopes (SRM) and Raman scattering. Hysteretic resistive switching behavior was observed in the samples that were studied with ON/OFF switching voltage equal to 8 - 10 V respectively. Simple empirical numerical simulation model, based on Deal-Grove model assumptions and mechanisms, for silver nanoclusters sulphidation process, was proposed.展开更多
Oxometallate(MO)-modified Ag clusters have attracted considerable research interest due to their aesthetic structures and fascinating properties.MOs can be a key factor in the organization of Ag ions into a complex en...Oxometallate(MO)-modified Ag clusters have attracted considerable research interest due to their aesthetic structures and fascinating properties.MOs can be a key factor in the organization of Ag ions into a complex entity in an ordered way.Enormous effort has been devoted to exploiting the synthetic strategy of MO–Ag cluster hybrid nanocomposites.Herein,we intend to review the recent progress in the design and construction of MO–Ag clusters with daedal architectures and potential applications.Accordingly,six different types of MO–Ag clusters are summarized mainly in terms of array configurations:(1)MOs@Ag shells;(2)Ag core@MOs;(3)Ag core@MOs@Ag shells;(4)coordination polymers;(5)intercluster compounds and(6)mixed array configurations.Besides,the synergistic effects between MOs and Ag clusters are presented.Based on the current development in this area,this minireview is expected to provide a perspective on controllable preparation of MO–Ag clusters,and a basic understanding of the structure/property correlations of Ag nanoparticle-metal oxide materials,thereby assisting in building functional nanomaterials.展开更多
基金supported by the National Natural Science Foundation of China(21203027,21073035,21373048)Funds of Fujian Province(2012J01032,2012J01041)Fuzhou University(2012-XQ-11)
文摘Density functional theory calculations have been performed to study the interaction of small silver clusters, Ag2-Ag9, with HCN. The adsorption of HCN on-top site of the silver cluster, among various possible sites, is energetically preferred. The adsorption energies of HCN on the silver clusters reach a local maximum at n = 4, which is only about 0.450 eV, indicating that the adsorbed HCN molecule is weakly perturbed. The adsorbed C-N and C-H stretching frequencies are blue- and red-shifted compared with the values of free HCN, respectively.
文摘The interactions between AgnO- （n=1-8） and H2 （or D2） were explored by combination of the mass spectroscopy experiments and density function theory （DFT） calculations. The experiments found that all oxygen atoms in AgnO- （n--1-8） are inert in the interactions with H2 or D2 at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation （PROX） of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between AgnO- （n=1-8） and H2 were explored using DFT calculations. The results indicated that adsorption of H2 on any site of AgnO- （n=1-8） is extremely weak, and oxidation of H2 by any kind of oxygen in AgnO- （n=1-8） has an apparent barrier strongly dependent on the adsorption style of the ＂O＂. These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.
基金Financial support of National Natural Science Foundation of China(No.21271090)Coordination Chemistry State key Laboratory Foundation of Nanjing University
文摘New types of fluorescence DNA-based silver nanoclusters（DNAn-Ag NCs, n = 1, 2, 3c, 4c, 5c） were synthesized by C3T-rich nucleotides as templates. It is found that the assembly of DNAn-Ag NCs with nucleotides containing GAG sequences produce silver clusters with an enhanced red emission. Results indicate that GAG is the good enhancer of DNAn-Ag NCs constructed by C3T-rich nucleotides. The fluorescence titration reveals that enhanced red emission is sensitive to Fe（Ⅲ/Ⅱ） ions with the formation of non-emission nanoclusters. Thus, the GAG-containing nucleotide can be an enhancer for the emission of silver clusters with C3T-rich nucleotide and a mediator of the iron-cluster interplay.
基金Project supported by CNPq,CAPES,and FAPES(Brazilian Agencies)
文摘At the Douglas-Kroll-Hess （DKI4） level, the B3PW91 functional along with the all-eleclron relativistic basis sets of valence triple and quadruple zeta qualities are used to determine the structure, stability, and electronic properties of the small silver clusters （Agn, n ≤ 7）. The results presented in this study are in good agreement with the experimental data and theoretical values obtained at a higher level of theory from the literature. Static polarizability and hyperpolarizability are also reported. It is verified that the mean dipole polarizability per atom exhibits an odd-even oscillation and that the polarizability anisotropy is directly related to the cluster shape. In this article, the first study of hyperpolarizabilities of small silver clusters is presented. Except for the monomer, the second hyperpolarizabilities of the silver clusters are significantly larger than those of the copper clusters.
基金supported by the NSFC(21771113,21531005,and 21421001)the Nature Science Fund of Tianjin,China(16JCZDJC36900).
文摘Fruitful efforts have been made for the assembly of nanosized silver clusters,and the majority of which are protected by thiolates and alkynyl ligands.By comparison,the reported silver clusters or silvercluster-based supramolecular networks protected by N-donor ligands are very rare because of the hard basicity of N-donor ligands with respect to the soft acid Ag(Ⅰ).Here,by using an N-donor ligand,a 2D Cl@Ag_(11)N_(24)-based supramolecular network[Cl@Ag_(11)(L)_(8)X_(2)]_(n)(X=CF_(3)COO^(-)for 1,NO_(3)^(-)for 2 and CF_(3)SO_(3)^(-)for 3)has been constructed with a Ag-O bond as the linker.This high-nuclearity silver cluster Cl@Ag_(11)N_(24) has an open dendritic structure with a high coordination ratio of the N atom,which is different from the well-established macrocycle,spheroidal cage and core-shell architectures based on silver-thiolate/alkynyl/phosphine clusters.The stability and assembly process of the 2D network has been studied by high-resolution electrospray mass spectrometry(HR-ESI-MS).Notably,1 shows an intriguing dual-emission feature that is strongly influenced by different excitation wavelengths and temperatures.Significantly,this work sheds new light on the construction of novel silver clusters and supramolecular networks based on them and provides a kind of luminescent material.
基金supported by the National Natural Science Foundation of China(grant nos.22325105,52261135637,22201159,22171164,92361301)the Natural Science Foundation of Shandong Province(grant nos.ZR2019ZD45,ZR2020ZD35,ZR2022QB008)the Instrument Improvement Funds of Shandong University Public Technology Platform(grant no.ts20220102).M.A.acknowledge the financial support through the Researchers Supporting Project number(grant no.RSP2024R147),King Saud University,Riyadh,Saudi Arabia.The Center for Structural and Property Analysis of Shandong University for analytical characterization is also acknowledged.
文摘Metal clusters with circularly polarized luminescent(CPL)activity have potential applications in security encoding,encrypted transmission,information stor-age,and so on.However,constructing CPL-active metal clusters on a large scale using self-assembly-based synthetic approaches has been challenging.Herein,we present a collaborative strategy to assem-ble a chiral cyclic hydrogen-bonding(HB)platform(γ-cyclodextrin(γ-CD))onto a photoluminescent sil-ver cluster to form a supramolecular adduct(Ag_(6)@γ-CD).The Ag6@γ-CD fully leverages the advantages of its individual components and exhibits notable CPL activity.Single-crystal X-ray diffraction and sys-tematic photoluminescence investigation reveal that the cyclic HB motif formed between Ag_(6)andγ-CD effectively promotes the population of the first ex-cited state(S 1)and facilitates supramolecular chiral transfer fromγ-CD to Ag_(6),resulting in the boosted CPL lighting.Furthermore,the decagram-scale synthesis of a functionalized adduct has been accomplished using mechanochemistry techniques,providing a material guarantee for the practical applications.
基金supported by the National Natural Science Foundation of China(Nos.22488101 and 22071274).
文摘Aggregation-induced emission(AIE)and thermally activated delayed fluorescence(TADF)are two optoelectronic properties with great potential for applications.However,metal nanoclusters exhibiting both AIE and TADF characteristics have not been extensively studied.This study investigates a binary cocrystal system based on silver nanoclusters—Ag_(6)(Et_(2)NCS_(2))6·[Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6]_(2)(1-Ag_(6)·(Ag_(11))_(2)),aiming to explore the synergistic effects between flexible-alkyl dithiol and rigid monothiol ligands.Due to the introduction of Ag_(6)structures,the system exhibits enhanced stability and modulated optical properties.The binary tricluster 1-Ag_(6)·(Ag_(11))_(2)demonstrates significant AIE behavior,with an approximately 15-fold increase in intensity when the water volume fraction(fw)is 60%.Single-crystal X-ray diffraction analysis indicates that the enhanced AIE effect originates from intercluster hydrogen bonding interactions,which drive the self-assembly of sub-clusters and form hierarchical structures,thereby suppressing ligand rotation.In addition,the system exhibits the TADF phenomenon in the temperature range of 100−175 K.In order to further investigate the effect of ligand variations on optical properties,two unitary clusters,Ag_(11)(AdmS)_(3)(Et_(2)NCS_(2))6(2-Ag_(11)-AS)and Ag_(11)(tBuS)_(3)(Et_(2)NCS_(2))6(3-Ag_(11)-BS),are synthesized,and their roles in regulating optoelectronic properties are explored through ligand exchange reactions.This study provides important insights for the development of efficient luminescent materials with AIE and TADF properties,highlighting the critical roles of ligand exchange and structural configuration.
基金financially supported by the National Natural Science Foundation of China(Nos.21871025,21831001)the Recruitment Program of Global Experts(Young Talents)Beijing Institute of Technology(BIT)Excellent Young Scholars Research Fund.
文摘Comparing to the conventional polyoxometalate(POM)-templated silver(Ag)clusters,asymmetrically covered POM-templated Ag clusters have been rarely reported.In this work,a new Ag cluster,H[Co(SiW_(11)O_(39))Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))@Ag_(37)(^(t)BuC≡C)_(23)(NO_(3))_(2)(DMF)_(3)](Ag_(37)Co_(5)),has been successfully prepared using a facile solvothermal approach.Such a unique asymmetrical architecture is ascribed to the uneven charge distribution of the in situ generated[Co(SiW_(11)O_(39))]^(6-)and[Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))]^(7-)moieties,leading to the asymmetrical coverage of alkynyl-protected Ag shell.Various physicochemical and catalytic studies revealed that the resulting solid-state Ag_(37)Co_(5) crystals exhibited interesting temperature-dependent photoluminescence property,efficient and recyclable photothermal conversion ability,and good catalytic activity towards the detoxication of 4-nitrophenol.
基金supported by the National Natural Science Foundation of China(22471017,21831001,22001016)the China Postdoctoral Science Foundation(2020TQ0038)+1 种基金the Recruitment Program of Global Experts(Young Talents)the Beijing Institute of Technology(BIT)Excellent Young Scholars Research Fund.
文摘Establishing the correlation between inter-cluster assembly and auxiliary ligands at the atomic level is crucial for the development of metal cluster science.In this work,we report the successful preparation and characterization of three Ag clusters,discrete 0-D Ag_(51)S_(6)Cl_(3)(i PrS)_(21)(TsO)_(15)CH_(3)CN(0-D Ag_(51),i PrS–=isopropanethiolate,TsO–=toluenesulfonate),1-D{Ag_(38)S_(4)-(i PrS)_(18)(PhCOO)_(12)}n(1-D Ag_(38),PHCOO–=benzoate),and 2-D{Ag_(2)0(SO_(4))Cl_(2)(i PrS)10(NO_(3))6}n(2-D Ag_(20)),using a delicate auxiliary-ligand-induced strategy.Structural analyses reveal that the types of auxiliary ligands can readily affect the structure and dimensionality of resulting Ag clusters.The addition of different surface auxiliary ligands from TsO–to PhCOO–and then to NO_(3)–leads to the formation of 0-D Ag_(51) to 1-D Ag_(38) and then to 2-D Ag_(2)0 clusters under otherwise identical reaction conditions,respectively.The resulting Ag clusters exhibited structure-related optical/luminescence properties and distinct bathochromic shifts as revealed by the temperature-dependent luminescence and single-crystal X-ray diffraction studies.
基金National Natural Science Foundation of China,Grant/Award Number:92061201 U21A20277Thousand Talents(Zhongyuan Scholars)Program of Henan Province,Grant/Award Number:234000510007Excellent Youth Foundation of Henan Scientific Committee,Grant/Award Number:232300421022。
文摘The development of stimuli-responsive circularly polarized luminescence(CPL)materials is quite attractive but challenging.Here,a pair of atomically precise enan-tiomers R/S-Ag20 nanoclusters has been synthesized using chiral acid ligands.And then,stimuli-responsive CPL materials were developed by assembling the chiral silver nanoclusters with an achiral bridging ligand.The atomically precise silver cluster-assembled materials produce CPL with a dissymmetry factor(|glum|)of 1×10-3,through the high-efficiency chiral induction process.More interestingly,the single CPL band at room temperature could quickly transform into highly separated dual CPL emissions at low temperature.This study provides a new strategy for the rational functionalization of chiral silver clusters in preparing cluster-based CPL emitters and enriches the types of stimuli-responsive CPL materials.
基金the“Thousand Talents Program”of Chinathe National Natural Science Foundation of China(No.21101170 and 21573139)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Research Funds of Shaanxi Normal University。
文摘In this work,three stable dumbbell-shaped silver clusters 1~3,formed by a novel bifunctional ligand Ph2P-C6H4-3-C=CH,are presented.All three complexes have cage structures constructed with thirty-six silver atoms,which are templated by chloride anions.During the self-assembly process of silver acetylides,argentophilic interactions and Ag(I)-ethynide interactions are important for the formation of silver cores to yield a diversity of silver clusters.Weak molecular interactions(π-π,C-H…π,C-H…F,C-H…O)are also found in these complexes,which are crucial to stabilizing these silver clusters.Compared with simple alkynyl ligands(RC≡C-),the introduction of phosphine groups into alkynyl ligand can effectively control the undesired infinite growth of silver acetylides.The photophysical behaviors of complexes 1~3 are studied,showing intense orange roomtemperature luminescence in the solid state upon the exposure to UV light.The luminescence mainly arises from ligand-to-metal charge transfer(LMCT)and metal-cluster-centered transitions(MC)within the silver clusters.
基金supported by the Postdoctoral Science Foundation of Central South University
文摘A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.
基金supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(Nos.KJQN201801602,KJQN201801607)the Basic and Frontier Research Project of Chongqing Science and Technology Commission(No.cstc2018jcyjAX0110)+1 种基金the Key Laboratory for Green Chemical Technology of Chongqing University of Education(No.2016xjpt08)the Research Project of Chongqing University of Education(Nos.JG2017015,KY20180241,YX-2019-01)
文摘A tetrahedral silver(I) cluster complex {Ag4[HC(PPh2)3](S2PPh2)3}ClO4(1,HC(PPh2)3 = 1,1,1-tris(triphenylphosphino)methane, S2PPh2 = diphenyldithiophosphinate) was synthesized by assembling silver ion with phosphor and sulphur mixed-ligand system. The complex was characterized by single-crystal X-ray crystallography, high-resolution mass spectroscopy and thermal analysis. In the crystal structure, an inverted tetrahedron was constructed from Ag4 metal skeleton. The Ag4 cage was stabilized by three diphenyldithiophosphinate ligands and one 1,1,1-tris(triphenylphosphino)methane ligand. 1 exhibits luminescent properties in solid state. A bright yellow-green emission centered at 533 nm has been observed in solid state. Large Stokes' shifts with long range of emissive lifetime indicate that the emission likely originates from a triplet state parentage.
基金supported by the National Natural Science Foundation of China (21671175)the Program for Science & Technology Innovation Talents in Universities of Henan Province (164100510005)the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (19IRTSTHN022) and Zhengzhou University
文摘A new 1D silver cluster-assembled complex Ag_(10)bpy-CH_3CN exhibiting intense photoluminescence was reported. Upon the loss of coordinated acetonitrile, Ag_(10)bpy-CH_3CN form Ag_(10)bpy with Ag_(10)S_6 cores slightly distorted, being accompanied with photoluminescence quenching. Inverse process can be realized by treating Ag_(10)bpy with acetonitrile and shows a selectively erasable photoluminescent switch.
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Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.
文摘Resistive switching Ag/Ag2S nanoclusters were formed by sulphidation of melting-dispersed thin and continuous Ag films. The morphology, structure and electrical properties of the prepared clusters were characterized by scanning (SEM), transmitting electron (TEM), scanning resistance microscopes (SRM) and Raman scattering. Hysteretic resistive switching behavior was observed in the samples that were studied with ON/OFF switching voltage equal to 8 - 10 V respectively. Simple empirical numerical simulation model, based on Deal-Grove model assumptions and mechanisms, for silver nanoclusters sulphidation process, was proposed.
基金supported by the National Natural Science Foundation of China(22201038,22101048,21971038,22271046 and 21975044)the Fujian Provincial Department of Science and Technology(2019H6012,21019L3004 and 2022J05040).
文摘Oxometallate(MO)-modified Ag clusters have attracted considerable research interest due to their aesthetic structures and fascinating properties.MOs can be a key factor in the organization of Ag ions into a complex entity in an ordered way.Enormous effort has been devoted to exploiting the synthetic strategy of MO–Ag cluster hybrid nanocomposites.Herein,we intend to review the recent progress in the design and construction of MO–Ag clusters with daedal architectures and potential applications.Accordingly,six different types of MO–Ag clusters are summarized mainly in terms of array configurations:(1)MOs@Ag shells;(2)Ag core@MOs;(3)Ag core@MOs@Ag shells;(4)coordination polymers;(5)intercluster compounds and(6)mixed array configurations.Besides,the synergistic effects between MOs and Ag clusters are presented.Based on the current development in this area,this minireview is expected to provide a perspective on controllable preparation of MO–Ag clusters,and a basic understanding of the structure/property correlations of Ag nanoparticle-metal oxide materials,thereby assisting in building functional nanomaterials.
