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
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
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
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
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
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
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
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
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
Two structurally characterized metal-cluster-centered supramolecular architectures named [Ag8（1,2-（C= C）2-C6H4）（Py[6]）（CF3CO2）6]·2.5MeOH （1） and [Ag12（1,2,4,5-（C=C）aC6H2）（Py[6]）2（CF3SO3）s]·...Two structurally characterized metal-cluster-centered supramolecular architectures named [Ag8（1,2-（C= C）2-C6H4）（Py[6]）（CF3CO2）6]·2.5MeOH （1） and [Ag12（1,2,4,5-（C=C）aC6H2）（Py[6]）2（CF3SO3）s]·4MeOH·3H2O （2） are synthesized through the interaction with a bowl-shaped macrocyclic ligand PyI61. Particularly, two dissimilar silver（I） clusters are resulted in 2 within the structure under the influence of the macrocyclic ligand Py[6]. Such dissimilarity of the silver（1） cluster is also reflected on the structural and photophysical differences between 1 and 2.展开更多
Engineering the surface of the metal clusters with the core structure maintained and tuning their luminescence in a wide range is still a challenge in the nanomaterial research.We modified six mono-pyridyl ligands wit...Engineering the surface of the metal clusters with the core structure maintained and tuning their luminescence in a wide range is still a challenge in the nanomaterial research.We modified six mono-pyridyl ligands with different electronic effects(conjugation effect or induction effect)on a superatomic silver cluster[Ag_(14)(C_(2)B_(10)H_(10)S_(2))_(6)(CH_(3)CN)_(8)](denoted as Ag_(14))through in situ site-specific surface engineering.展开更多
Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents,which usually serve as the starting point for the preparation of clusters.However,such a...Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents,which usually serve as the starting point for the preparation of clusters.However,such a process is still far from clear.Herein,we report the controlled synthesis of silver-t-butylthiolate clusters from reactions of polymeric[Ag^(t)BuS]n and suitable templates in the presence of solubilizing reagents to offer a detailed look at the mechanism of cluster’s formation.As the provided solubilizing reagents have weak coordina-tion ability,such as O-or N-donating ligands,the obtained polymeric compound retains the linear structure pat-tern that S and Ag atoms are arranged alternately.When extra templates NO_(3)^(−)and CO_(3)^(2−)are applied,the disk-like clusters Ag_(19)and Ag_(20)are constructed with the same[Ag^(t)BuS]_(5)circles that may directly cyclize from the linear[Ag^(t)BuS]_(n)fragments.In contrast,(EtO)_(2)PS_(2)^(−)and(iPrO)_(2)PS_(2)^(−)anions have large size and strong coordination abil-ity rendering the structure of the polymer completely fragmented.Thus extremely short[Ag^(t)BuS]n pieces with silver ions and solubilizing ligands assemble around the templates V_(2)O_(7)^(4−)and W_(2)O_(9)^(4−),leading to the formation of clusters Ag_(22)and Ag_(24).展开更多
The combination of CrO4^2-anion and N,N′-dimethylformamide(DMF)-containing solvent helps to stabilize an atom-precise ultrasmall Ag6 kernel into a 52-nuclei silver shell,giving a core-shell Ag6@Ag52 wheel-like struct...The combination of CrO4^2-anion and N,N′-dimethylformamide(DMF)-containing solvent helps to stabilize an atom-precise ultrasmall Ag6 kernel into a 52-nuclei silver shell,giving a core-shell Ag6@Ag52 wheel-like structure(SD/Ag58b).The solution behavior and photocurrent response property were investigated in details.展开更多
Although inorganic anion templates are highly appreciated in the synthesis of nanosized silver clusters,supramolecular clusters used as templates to mold silver nanoclusters remain as-yet-unknown due to their existenc...Although inorganic anion templates are highly appreciated in the synthesis of nanosized silver clusters,supramolecular clusters used as templates to mold silver nanoclusters remain as-yet-unknown due to their existence as volatile forms in solution.Here,we report the synthesis of a novel silver-thiolate nanocluster(SD/Ag58a),comprising an outer tetrahedral cage of 58 silver atoms and a central supramolecular cluster[CH_(3)OH@(SO_(4))_(4)(H_(2)O)6]8−(hereafter abbreviated as CS_(4)H_(6)).Ternary CS_(4)H_(6) cluster was constructed from an(SO_(4))_(4) tetrahedron encaging one CH_(3)OH molecule inside and six water molecules sitting between paired SO_(4)^(2−)ions to form the[SO_(4)…H_(2)O…SO_(4)]hydrogen bonds(H-bonds).Also,the CS4H6 could coordinate to the inner wall of the Ag58 cage by forming Ag-O bonds,exerting templating effect on the formation of SD/Ag58a.Moreover,SD/Ag58a showed a photocurrent response upon visible light irradiation and emitted luminescence in the near-infrared(NIR)region at a cryogenic temperature.This work exemplifies the ternary supramolecule templating effect in the construction of silver nanocluster and facilitates understanding of the structure of complex solvated anion cluster in atomic precision.展开更多
In this study,the size of the titanium organic cage was controlled to achieve the restricted growth from a single Ag(I)atom(Ag@Ti_(5))to rare all-carboxylate-protected superatomic Ag cluster(Ag6@Ti_(6)).The classical ...In this study,the size of the titanium organic cage was controlled to achieve the restricted growth from a single Ag(I)atom(Ag@Ti_(5))to rare all-carboxylate-protected superatomic Ag cluster(Ag6@Ti_(6)).The classical octahedral Ag_(6)^(4+) cluster with two delocalized electrons(2e)has been encapsulated in a Ti6 organic cage,which shows high stability in air and dimethyformamide(DMF).Furthermore,larger 2e nested double-tetrahedra Ag clusters(Ag_(8)^(6+) and Ag_(9)^(7+))protected using a tetrahedral hollow metalloligand framework(Ag_(8)@Ti_(4) and Ag_(9)@Ti_(4))were obtained.Electrospray ionization mass spectrometry(ESI-MS)and density functional theory(DFT)calculations confirmed that there are two delocalized electrons on these small Ag clusters.This study provides a new form of protection for superatomic Ag clusters and provides a feasible strategy for the development of stable Ag clusters.展开更多
Isolating reductive silver kernel from shell is a challenging task but is quite important to understand the embryonic form during the formation of silver nanoclusters.The intercalation of suitable anionic species may ...Isolating reductive silver kernel from shell is a challenging task but is quite important to understand the embryonic form during the formation of silver nanoclusters.The intercalation of suitable anionic species may be of benefit for passivating then capturing such highly active kernel.Herein,we successfully isolated a novel silver thiolate nanocluster[Ag_(13)@Ag_(76)S_(16)(Cyh S)_(42)(p-NH_(2)-Ph As O_(3))_(4)]^(3+)(SD/Ag89 a,Cyh SH=cyclohexanethiol)that contains a well-isolated icosahedral Ag_(13) kernel passivated by four Ag S_(4)^(7-) tetrahedra and four p-NH_(2) Ph As O_(3)^(2-) piercing from outer Ag_(72) shell.Of note,this Ag_(13) kernel is the largest isolable subvalent silver kernel beneath the silver shell with extremely legible core-shell boundary ever before and represents a precise embryonic model formed in the reducing Ag(I)to Ag(0)followed by aggregating to large silver nanoparticles.The reductive role of DMF and the introduction of anionic passivation layer(APL)synergistically modulate the reduction kinetics,facilitating the capture of ultrasmall subvalent silver kernel.SD/Ag89 a emits in near infrared(NIR)region(λ_(em)=800 nm)at low temperature.The synthetic strategy shown in this work opens up new opportunities for precisely capturing and recognizing diverse reductive silver kernels in different systems.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 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.
文摘Two structurally characterized metal-cluster-centered supramolecular architectures named [Ag8（1,2-（C= C）2-C6H4）（Py[6]）（CF3CO2）6]·2.5MeOH （1） and [Ag12（1,2,4,5-（C=C）aC6H2）（Py[6]）2（CF3SO3）s]·4MeOH·3H2O （2） are synthesized through the interaction with a bowl-shaped macrocyclic ligand PyI61. Particularly, two dissimilar silver（I） clusters are resulted in 2 within the structure under the influence of the macrocyclic ligand Py[6]. Such dissimilarity of the silver（1） cluster is also reflected on the structural and photophysical differences between 1 and 2.
基金This work was supported by the National Science Fund for Distinguished Young Scholars(No.21825106)the National Natural Science Foundation of China(No.21671175)the Program for Innovative Research Team(in Science and Technology)in Universities of Henan Province(No.19IRTSTHN022)and Zhengzhou University.
文摘Engineering the surface of the metal clusters with the core structure maintained and tuning their luminescence in a wide range is still a challenge in the nanomaterial research.We modified six mono-pyridyl ligands with different electronic effects(conjugation effect or induction effect)on a superatomic silver cluster[Ag_(14)(C_(2)B_(10)H_(10)S_(2))_(6)(CH_(3)CN)_(8)](denoted as Ag_(14))through in situ site-specific surface engineering.
基金supported by the National Natural Science Foundation of China (No. 21771071, 22171094, and 21925104)the Key Scientific Research Projects of Universities in Henan Province (No. 21A150060)
文摘Silver thiolate polymers are intercepted to form different structural fragments when reacting with variant solubilizing reagents,which usually serve as the starting point for the preparation of clusters.However,such a process is still far from clear.Herein,we report the controlled synthesis of silver-t-butylthiolate clusters from reactions of polymeric[Ag^(t)BuS]n and suitable templates in the presence of solubilizing reagents to offer a detailed look at the mechanism of cluster’s formation.As the provided solubilizing reagents have weak coordina-tion ability,such as O-or N-donating ligands,the obtained polymeric compound retains the linear structure pat-tern that S and Ag atoms are arranged alternately.When extra templates NO_(3)^(−)and CO_(3)^(2−)are applied,the disk-like clusters Ag_(19)and Ag_(20)are constructed with the same[Ag^(t)BuS]_(5)circles that may directly cyclize from the linear[Ag^(t)BuS]_(n)fragments.In contrast,(EtO)_(2)PS_(2)^(−)and(iPrO)_(2)PS_(2)^(−)anions have large size and strong coordination abil-ity rendering the structure of the polymer completely fragmented.Thus extremely short[Ag^(t)BuS]n pieces with silver ions and solubilizing ligands assemble around the templates V_(2)O_(7)^(4−)and W_(2)O_(9)^(4−),leading to the formation of clusters Ag_(22)and Ag_(24).
基金supported by the National Natural Science Foundation of China(21822107,21571115,21827801,21671172)the Natural Science Foundation of Shandong Province(JQ201803,ZR2017MB061)+2 种基金the Taishan Scholar Project of Shandong Province of Chinathe Qilu Youth Scholar Funding of Shandong Universitythe Fundamental Research Funds of Shandong University(104.205.2.5)
文摘The combination of CrO4^2-anion and N,N′-dimethylformamide(DMF)-containing solvent helps to stabilize an atom-precise ultrasmall Ag6 kernel into a 52-nuclei silver shell,giving a core-shell Ag6@Ag52 wheel-like structure(SD/Ag58b).The solution behavior and photocurrent response property were investigated in details.
基金supported financially by the National Natural Science Foundation of China(grant nos.91961105,21822107,21571115,and 21827801)the Fok Ying Tong Education Foundation(grant no.171009)+3 种基金the Natural Science Foundation of Shandong Province(grant nos.ZR2020ZD35,ZR2019ZD45,JQ201803,and ZR2017MB061)the Taishan Scholar Project of Shandong Province of China(grant nos.tsqn201812003 and ts20190908)the Qilu Youth Scholar Funding of Shandong UniversityProject for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province(grant no.2019KJC028).
文摘Although inorganic anion templates are highly appreciated in the synthesis of nanosized silver clusters,supramolecular clusters used as templates to mold silver nanoclusters remain as-yet-unknown due to their existence as volatile forms in solution.Here,we report the synthesis of a novel silver-thiolate nanocluster(SD/Ag58a),comprising an outer tetrahedral cage of 58 silver atoms and a central supramolecular cluster[CH_(3)OH@(SO_(4))_(4)(H_(2)O)6]8−(hereafter abbreviated as CS_(4)H_(6)).Ternary CS_(4)H_(6) cluster was constructed from an(SO_(4))_(4) tetrahedron encaging one CH_(3)OH molecule inside and six water molecules sitting between paired SO_(4)^(2−)ions to form the[SO_(4)…H_(2)O…SO_(4)]hydrogen bonds(H-bonds).Also,the CS4H6 could coordinate to the inner wall of the Ag58 cage by forming Ag-O bonds,exerting templating effect on the formation of SD/Ag58a.Moreover,SD/Ag58a showed a photocurrent response upon visible light irradiation and emitted luminescence in the near-infrared(NIR)region at a cryogenic temperature.This work exemplifies the ternary supramolecule templating effect in the construction of silver nanocluster and facilitates understanding of the structure of complex solvated anion cluster in atomic precision.
基金This work was supported by the National Science Fund for Distinguished Young Scholars(No.21825106)the National Natural Science Foundation of China(Nos.21975065 and 21671175)+1 种基金the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.164100510005)the Program for Innovative Research Team(in Science and Technology)in Universities of Henan Province(No.19IRTSTHN022)and Zhengzhou University.
文摘In this study,the size of the titanium organic cage was controlled to achieve the restricted growth from a single Ag(I)atom(Ag@Ti_(5))to rare all-carboxylate-protected superatomic Ag cluster(Ag6@Ti_(6)).The classical octahedral Ag_(6)^(4+) cluster with two delocalized electrons(2e)has been encapsulated in a Ti6 organic cage,which shows high stability in air and dimethyformamide(DMF).Furthermore,larger 2e nested double-tetrahedra Ag clusters(Ag_(8)^(6+) and Ag_(9)^(7+))protected using a tetrahedral hollow metalloligand framework(Ag_(8)@Ti_(4) and Ag_(9)@Ti_(4))were obtained.Electrospray ionization mass spectrometry(ESI-MS)and density functional theory(DFT)calculations confirmed that there are two delocalized electrons on these small Ag clusters.This study provides a new form of protection for superatomic Ag clusters and provides a feasible strategy for the development of stable Ag clusters.
基金supported by the National Natural Science Foundation of China(91961105,21822107,21827801)the Fok Ying Tong Education Foundation(171009)+3 种基金the Natural Science Foundation of Shandong Province(ZR2019ZD45,JQ201803,ZR2020ZD35)the Taishan Scholar Project of Shandong Province of China(tsqn201812003,ts20190908)the Qilu Youth Scholar Funding of Shandong UniversityProject for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province(2019KJC028)。
文摘Isolating reductive silver kernel from shell is a challenging task but is quite important to understand the embryonic form during the formation of silver nanoclusters.The intercalation of suitable anionic species may be of benefit for passivating then capturing such highly active kernel.Herein,we successfully isolated a novel silver thiolate nanocluster[Ag_(13)@Ag_(76)S_(16)(Cyh S)_(42)(p-NH_(2)-Ph As O_(3))_(4)]^(3+)(SD/Ag89 a,Cyh SH=cyclohexanethiol)that contains a well-isolated icosahedral Ag_(13) kernel passivated by four Ag S_(4)^(7-) tetrahedra and four p-NH_(2) Ph As O_(3)^(2-) piercing from outer Ag_(72) shell.Of note,this Ag_(13) kernel is the largest isolable subvalent silver kernel beneath the silver shell with extremely legible core-shell boundary ever before and represents a precise embryonic model formed in the reducing Ag(I)to Ag(0)followed by aggregating to large silver nanoparticles.The reductive role of DMF and the introduction of anionic passivation layer(APL)synergistically modulate the reduction kinetics,facilitating the capture of ultrasmall subvalent silver kernel.SD/Ag89 a emits in near infrared(NIR)region(λ_(em)=800 nm)at low temperature.The synthetic strategy shown in this work opens up new opportunities for precisely capturing and recognizing diverse reductive silver kernels in different systems.
