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
A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group...A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group C2/c with a = 2.0448(3) nm, b= 1.5086(2) nm, c= 1.7923(2) nm, β=109.32(1)°. The structure of the title compound was solved by using 1 500 (I>3σ(I)) unique reflections and refined to R = 0.068. The structural features indicate the formal oxidation state of V(IV) + Ag (I), and partial charge transfer from Ag(I) to V(IV). The actions of reactants used in the reaction are discussed and a supposed formation process of the V2Ag2S4 cluster is suggested.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
The first crystal structural report of a AgDTC complex (DTC= dialkyldithiocarbamate, R= n butyl) presented in this paper shows that it is a hexanuclear species. The structural arrangement for the DDP (dialkyldi...The first crystal structural report of a AgDTC complex (DTC= dialkyldithiocarbamate, R= n butyl) presented in this paper shows that it is a hexanuclear species. The structural arrangement for the DDP (dialkyldithiophosphate) ligands is different from that of Cu 6(DDP) 6, but is the same as that of Ag 6 [SSP(O i Pr) 2] 6.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
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
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
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
The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniq...The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.展开更多
Supramolecular assembly is regarded as an effective strategy to endow metal clusters with rich and unique photophysical properties.However,the detailed mechanisms and influential factors for intercluster assemblies an...Supramolecular assembly is regarded as an effective strategy to endow metal clusters with rich and unique photophysical properties.However,the detailed mechanisms and influential factors for intercluster assemblies and their effects on luminescent properties remain unclear to date.In this work,we constructed a series of spirocyclic nonanuclear silver cluster compounds with varying alkyl chain lengths,which demonstrated distinct supramolecular assembly behaviors depending on temperature,concentration,and solvent polarity.展开更多
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Project supported by NNSFC and the Natural Science Foundation of Fujian.
文摘A novel heterometallic V2Ag2S4 thiocubane cluster was isolated from an assembly reaction system including (NH4)3VS4, Ag(PPh3)2NO3, OC4H8dtcNa and PhSNa in DMF. The title compound crystallizes in monoclinic space group C2/c with a = 2.0448(3) nm, b= 1.5086(2) nm, c= 1.7923(2) nm, β=109.32(1)°. The structure of the title compound was solved by using 1 500 (I>3σ(I)) unique reflections and refined to R = 0.068. The structural features indicate the formal oxidation state of V(IV) + Ag (I), and partial charge transfer from Ag(I) to V(IV). The actions of reactants used in the reaction are discussed and a supposed formation process of the V2Ag2S4 cluster is suggested.
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.
基金ProjectsupportedbytheNaturalScienceFoundationofGuangdongProvince (No .990 4 63)andtheNationalNaturalScienceFounda tionofChina (No .2 95 6 10 0 2 )
文摘The first crystal structural report of a AgDTC complex (DTC= dialkyldithiocarbamate, R= n butyl) presented in this paper shows that it is a hexanuclear species. The structural arrangement for the DDP (dialkyldithiophosphate) ligands is different from that of Cu 6(DDP) 6, but is the same as that of Ag 6 [SSP(O i Pr) 2] 6.
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 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 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.
文摘The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.
基金National Natural Science Foundation of China(NNSFCgrant nos.22025105,21772111,21821001,and 91956125).
文摘Supramolecular assembly is regarded as an effective strategy to endow metal clusters with rich and unique photophysical properties.However,the detailed mechanisms and influential factors for intercluster assemblies and their effects on luminescent properties remain unclear to date.In this work,we constructed a series of spirocyclic nonanuclear silver cluster compounds with varying alkyl chain lengths,which demonstrated distinct supramolecular assembly behaviors depending on temperature,concentration,and solvent polarity.
