Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially s...Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.展开更多
The ring-opening polymerization （ROP） of ε-caprolactone （ε-CL） using lanthanide thiolate complexes [（CH3CsH4）2Sm（μ-SPh）（THF）]2 （1） and Sm（SPh）3（HMPA）3 （2） as initiators has been investigated for t...The ring-opening polymerization （ROP） of ε-caprolactone （ε-CL） using lanthanide thiolate complexes [（CH3CsH4）2Sm（μ-SPh）（THF）]2 （1） and Sm（SPh）3（HMPA）3 （2） as initiators has been investigated for the first time. Both of 1 and 2 were found to be highly efficient initiators for the ROP of ε-CL. The poly（ε-caprolactone） （PCL） with molecular weight Mn up to 1.97 ×10^5 and relatively narrow molecular weight distributions （1.20〈MW/Mn〈 2.00） have been obtained in high yield in the temperature range of 35-65℃. According to the polymer yield, 2 showed much higher activity than 1. However, the number-average molecular weight of PCL obtained with 2 was much lower than with 1. The possible polymerization mechanism of the ε-CL polymerization has been proposed based on the results of the end group analysis of the ε-CL oligomer.展开更多
Thiolate(SR)-protected gold nanoclusters(Aun(SR)m NCs)are a rare type of material capable of simultaneously exhibiting multiple physicochemical properties well-suited to specific applications,including photoluminescen...Thiolate(SR)-protected gold nanoclusters(Aun(SR)m NCs)are a rare type of material capable of simultaneously exhibiting multiple physicochemical properties well-suited to specific applications,including photoluminescence,thermocatalysis,electrocatalysis,photocatalysis,magnetism,and optical activity.Over the past several decades,there has been tremendous progress in our understanding of the structure and physicochemical properties of Aun(SR)m NCs,resulting in the ability to fine-tune the characteristics of these materials.It is therefore helpful to examine the extent to which the properties of Aun(SR)m and related metal NCs can now be adjusted based on design.This review presents representative examples of previous studies concerning the geometry,electronic structure,luminescence properties,catalysis,magnetism and optical activity of Aun(SR)m and related metal NCs and discusses the current status of the designability of these NCs to impart specific structural and physicochemical characteristics.This information is expected to accelerate the fabrication of highly functional materials based on Aun(SR)m and related metal NCs.展开更多
A novel type of thermal stabilizer-antimony tris (thioethyl stearate) (ATS) was synthsized. Its thermal stability was measured by heat-aging oven test when incorporated into PVC. ATS was synthesized from stearic acid,...A novel type of thermal stabilizer-antimony tris (thioethyl stearate) (ATS) was synthsized. Its thermal stability was measured by heat-aging oven test when incorporated into PVC. ATS was synthesized from stearic acid, antimony trioxide and 2-mercaptoethanol in two steps. The reaction conditions of synthesis were optimized through orthogonal test. Experimental results show that the molar ratio of stearic acid and antimony tris (2-hydroxyethylthiolate) was 1.2, adding 0.6%tetra-n-butyl titanate as catalyst and xylene as azeotropic solvent, heating and refluxing for about 4 h, and the yield of ATS is 83.9%. The thermal stability time is about 40 min(at 200 °C) when added 2phr(per hundred resin) in PVC. The thermal stability of ATS is better than that of Ca-Zn complex and basic lead stabilizers, and equal to that of dibutyltin dilaurate.展开更多
By using a unique temperature-dependent,chloride-mediated approach,two atom-precise silver nanoclusters[Cl@Ag_(14)(Tab)_(12)-(C_(5)H_(4)NCl)_(12)](PF_(6))_(13)(Cl@Ag_(14))and[Cl_(3)@Ag_(24)(Tab)_(20)(C_(5)H_(4)NCl)_(1...By using a unique temperature-dependent,chloride-mediated approach,two atom-precise silver nanoclusters[Cl@Ag_(14)(Tab)_(12)-(C_(5)H_(4)NCl)_(12)](PF_(6))_(13)(Cl@Ag_(14))and[Cl_(3)@Ag_(24)(Tab)_(20)(C_(5)H_(4)NCl)_(11)]Cl(PF_(6))_(20)(Cl_(3)@Ag_(24))(Tab=4-(trimethylammonio)benzenethiolate,C_(5)H_(4)NCl=3-chloropyridine)were obtained successfully.Notably,the number of chloride ions encapsulated inside the Ag-S shell could be regulated by the slow dissolution of almost insoluble KCl at various temperatures.The inclusion of additional core chloride ions results in the expansion of the surrounding Ag-S shell.This article provides a promising synthetic approach for controlling the number of Ag atoms that form a shell around the anionic core,in addition to offering a potential pathway for the introduction of other inorganic anions into silver clusters.More broadly,through the use of related ligands,the synthetic strategy offers scope for generating new families of silver thiolate clusters of varying size and composition.展开更多
Two atom-precise silver nanoclusters[Ag_(25)Cl_2(Tab)_(14)(Ph COO)_(11)(DMF)_4](PF_6)_(12)(Ag_(25),DMF=N,N-dimethylformamide)and[Ag_(26)Cl_2(Tab)_(14)(Ph COO)_(13)(DMAc)_4](PF_6)_(11)(Ag_(26),DMAc=N,N-dimethylacetamid...Two atom-precise silver nanoclusters[Ag_(25)Cl_2(Tab)_(14)(Ph COO)_(11)(DMF)_4](PF_6)_(12)(Ag_(25),DMF=N,N-dimethylformamide)and[Ag_(26)Cl_2(Tab)_(14)(Ph COO)_(13)(DMAc)_4](PF_6)_(11)(Ag_(26),DMAc=N,N-dimethylacetamide)were synthesized based on the electrically neutral thiolate protective ligand,4-(trimethylammonio)benzenethiolate(Tab).The weak Ag–S interaction in Tab-protected silver nanoclusters allows to insert or leave a single silver atom in the Ag–S skeleton through solvent-trigger core fragmentation and re-arrangement,thereby realizing the reversible conversion of Ag_(25)and Ag_(26)for the first time.展开更多
[Co3(1,2-S2C6H4)3(PPh3)3][CoBr3(DMF)].sol (1, sol=CHCl3,O(C2H5)2,H2O) was obtained from the reaction of CoBr(PPh3)3 with Na2(S2C6H4) in chloroform. The Co3 core in the cation of 1 exhibits a metal-metal bonded isosce... [Co3(1,2-S2C6H4)3(PPh3)3][CoBr3(DMF)].sol (1, sol=CHCl3,O(C2H5)2,H2O) was obtained from the reaction of CoBr(PPh3)3 with Na2(S2C6H4) in chloroform. The Co3 core in the cation of 1 exhibits a metal-metal bonded isosceles triangle, in which the two longer Co-Co bonds are both bridged by S2C6H4 ligands on two sides of the triangle plane respectively, while the bottom short Co-Co bond is bridged by the third bidentate S2C6H4 ligand. A series of polynu-clear cobalt cluster compounds with phosphine, thiolate and/or sulphur ligands were prepared by low oxidation state Co+ with thiolates in organic solvents. These tri-, tetra-, hexa-, heptanuclear cluster compounds 1-8 with various types of crystal structures can be viewed as the condensed polynuclear cobalt complexes that the cobalt atom frameworks with sulphur bridged were built through the small triangular units of [Co3S3nL3] (n=1,2) with or without [CoL] (L=PR3, Br, Cl, 5-C5H5) fragments.展开更多
（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Co...（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 （C52H94S2Si4Er2 2） Mr = 1073.57 （1230.27）, a = 8.495（2） （8.41（2））, b = 26.913（8） （26.67（7））, c = 13.756（4） （13.68（4）） A, α = 90（90）, β = 101.184（5） （101.57（4））, γ = 90 （90）°, V= 3085.1（15） （3007（14）） A^3, Dc = 1.156 （1.359） g·cm^-3, Z= 2 （2）, F（000） = 1144 （1260）, μ = 2.046 （2.951） cm^-1, R = 0.0687 （0.0749） and wR = 0.1306 （0.1507） for observed reflections with I 〉 2σ（I）. X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C（^nBu） bond, forming a thiolate ligand.展开更多
A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occu...A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni（II） atom and the two silver（I） atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni（edt）2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581（11）,b = 12.239（9）,c = 22.316（17） ,β = 103.08（2）o,V = 3613（5） 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F（000） = 1604,T = 293（2） K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ（I）.展开更多
Two diiron dithiolate complexes [Fe2（CO）6（1,8-S2-2-CH2OOCPhC（10）H5）] 1 and[Fe2（CO）6（1,8-S2-2-CH2OOCPh-4-NO2C（10）H5）]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-r...Two diiron dithiolate complexes [Fe2（CO）6（1,8-S2-2-CH2OOCPhC（10）H5）] 1 and[Fe2（CO）6（1,8-S2-2-CH2OOCPh-4-NO2C（10）H5）]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ^1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe2S2 core with the Fe1–Fe2 distances of 2.5237（7）A in 1 and 2.5125（12）A in 2, falling in the normal range of Fe–Fe bond length（2.49 - 2.57 A）. The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at –1.074 V, –1.535 V（1） and –0.869 V, –1.247 V（2） vs. Fc/Fc^＋, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH3CN/NBu4PF6 solution.展开更多
Complex Fe_3(bdt)_3(PBu_3~n)_3 was synthesized in the presence of PBu_3~n and the structural regularities in a series of transition metal complexes containing bdtH_2 ligand were summarized. The title complex crystalli...Complex Fe_3(bdt)_3(PBu_3~n)_3 was synthesized in the presence of PBu_3~n and the structural regularities in a series of transition metal complexes containing bdtH_2 ligand were summarized. The title complex crystallizes in the triclinic space group P-, Mr=1195.19, cell parameters: a=13.283(3), b=20.115(5), c=13.156(3), (?)=90.33(2), β= 116.47 (1), γ=92.19(2)°, V=3143.5(2.7)~3, Z=2, d_c=1.26g/cm^3. The structure was solved by direct methods from 4122 unique reflections with I>4σ(I) and reached the final convergence factor of R(Rw) = 0.053 (0.060). The complex exhibits strong paramagnetism.展开更多
The title complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817（2）,b = 14.3...The title complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817（2）,b = 14.3889（2）,c = 15.2136（2） ,α = 71.018（1）,β = 74.911（1）,γ = 85.146（1）°,V = 2214.86（6） 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ（MoKα） = 0.616 mm-1,F（000） = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I 2σ（I） and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824（8）,2.3495（8） and 1.71（2）,respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.展开更多
Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crysta...Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.展开更多
The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF),...The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.展开更多
Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic s...Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic size" nanoclusters revealed a variety of unique structures such as decahedron, icosahedron, as well as hexagonal close packing(hcp) and body-centered cubic(bcc) packing arrangements in gold nanoclusters, which are largely different from the face-centered cubic(fcc) structure in conventional gold nanoparticles. The characteristic geometrical structures enable the nanoclusters to exhibit interesting properties, and these properties are in close correlation with their atomic structures according to the recent studies. Experimental and theoretical analyses have been applied in the structural identification aiming to clarify the universal principle in the structural evolution of nanoclusters. In this mini-review, we summarize recent studies on periodic structural evolution of fcc-based gold nanoclusters protected by thiolates. A series of nanoclusters exhibit one-dimensional growth along the [001] direction in a layer-by-layer manner from Au_(23)(TBBT)_(20) to Au_(36)(TBBT)_(24),Au_(44)(TBBT)_(28), and to Au_(52)(TBBT)_(32)(TBBT: 4-tert-butylbenzenethiolate). The optical properties of these nanoclusters also evolve periodically based on steady-state and ultrafast spectroscopy. In addition, two-dimensional growth from Au_(44)(TBBT)_(28) toward both [100] and [010] directions leads to the Au_(92)(TBBT)_(44) nanocluster, and the recently reported Au_(52)(PET)_(32)(PET: 2-phenylethanethiol) also follows this growth pattern with partial removal of the layer. Theoretical predictions of relevant fcc nanoclusters include Au_(60)(SCH_3)_(36), Au_(68)(SCH_3)_(40), Au_(76)(SCH_3)_(44), etc, for the continuation of 1 D growth pattern, as well as Au_(68)(SR)_(38)mediating the 2 D growth pattern from Au_(44)(TBBT)_(28) to Au_(92)(TBBT)_(44). Overall, this mini-review provides guidelines on the rules of structural evolution o展开更多
We reported the synthesis ofAul3o（SPh-Br）50（Br-Ph-SH=4-bromothiophenol） nanocluster with high purity and high yield via ＂size focusing＂ and ＂ligand exchange＂ processes. The time of synthetic process was signif...We reported the synthesis ofAul3o（SPh-Br）50（Br-Ph-SH=4-bromothiophenol） nanocluster with high purity and high yield via ＂size focusing＂ and ＂ligand exchange＂ processes. The time of synthetic process was significantly reduced compared with previous synthetic routine. AU130（SPh-Br）50 was determined by UV-Vis absorption spectros- copy and matrix-assisted laser desorption ionization（MALDI） mass spectroscopy. Thermo-gravimetric analysis （TGA） and size-exclusion chromatogram（SEC） analyses confirmed the purity of AU130（SPh-Br）50. The yield of gold nanoc- lusters was 20%（based on HAuCl4）.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
基金supported by the National Natural Science Foundation of China (21925303,21829501,21771186,22171268,22171267,21971246)the Anhui Provincial Natural Science Foundation(2108085MB56)+1 种基金the HFIPS Director’s Fund (BJPY2019A02,YZJJ202102,YZJJ202306-TS)the Collaborative Innovation Program of Hefei Science Center,Chinese Academy of Sciences (2020HSC-CIP005,2022HSCCIP018)。
文摘Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.
基金Project suported by the National Natural Science Foundation of China （No. 20272040）.
文摘The ring-opening polymerization （ROP） of ε-caprolactone （ε-CL） using lanthanide thiolate complexes [（CH3CsH4）2Sm（μ-SPh）（THF）]2 （1） and Sm（SPh）3（HMPA）3 （2） as initiators has been investigated for the first time. Both of 1 and 2 were found to be highly efficient initiators for the ROP of ε-CL. The poly（ε-caprolactone） （PCL） with molecular weight Mn up to 1.97 ×10^5 and relatively narrow molecular weight distributions （1.20〈MW/Mn〈 2.00） have been obtained in high yield in the temperature range of 35-65℃. According to the polymer yield, 2 showed much higher activity than 1. However, the number-average molecular weight of PCL obtained with 2 was much lower than with 1. The possible polymerization mechanism of the ε-CL polymerization has been proposed based on the results of the end group analysis of the ε-CL oligomer.
基金Japan Society for the Promotion of Science,Grant/Award Numbers:20H02698,20H02552,18H05178,20H05115Hydrogenomics,Grant/Award Number:21H00027+7 种基金Aquatic Functional Materials,Grant/Award Numbers:18H05178,22H04562Yazaki Memorial Foundation for Science and TechnologyOgasawara Foundation for the Promotion of Science and EngineeringKao Foundation for Arts and SciencesTEPCO Memorial FoundationJapan Science SocietyTakahashi Industrial and Economic Research FoundationKubota Corporation。
文摘Thiolate(SR)-protected gold nanoclusters(Aun(SR)m NCs)are a rare type of material capable of simultaneously exhibiting multiple physicochemical properties well-suited to specific applications,including photoluminescence,thermocatalysis,electrocatalysis,photocatalysis,magnetism,and optical activity.Over the past several decades,there has been tremendous progress in our understanding of the structure and physicochemical properties of Aun(SR)m NCs,resulting in the ability to fine-tune the characteristics of these materials.It is therefore helpful to examine the extent to which the properties of Aun(SR)m and related metal NCs can now be adjusted based on design.This review presents representative examples of previous studies concerning the geometry,electronic structure,luminescence properties,catalysis,magnetism and optical activity of Aun(SR)m and related metal NCs and discusses the current status of the designability of these NCs to impart specific structural and physicochemical characteristics.This information is expected to accelerate the fabrication of highly functional materials based on Aun(SR)m and related metal NCs.
文摘A novel type of thermal stabilizer-antimony tris (thioethyl stearate) (ATS) was synthsized. Its thermal stability was measured by heat-aging oven test when incorporated into PVC. ATS was synthesized from stearic acid, antimony trioxide and 2-mercaptoethanol in two steps. The reaction conditions of synthesis were optimized through orthogonal test. Experimental results show that the molar ratio of stearic acid and antimony tris (2-hydroxyethylthiolate) was 1.2, adding 0.6%tetra-n-butyl titanate as catalyst and xylene as azeotropic solvent, heating and refluxing for about 4 h, and the yield of ATS is 83.9%. The thermal stability time is about 40 min(at 200 °C) when added 2phr(per hundred resin) in PVC. The thermal stability of ATS is better than that of Ca-Zn complex and basic lead stabilizers, and equal to that of dibutyltin dilaurate.
基金supported by the National Natural Science Foundation of China (21871196, 21773163, 21531006)the Collaborative Innovation Center of Suzhou Nano Science and Technology+1 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Project of Scientific and Technologic Infrastructure of Suzhou (SZS201905)。
文摘By using a unique temperature-dependent,chloride-mediated approach,two atom-precise silver nanoclusters[Cl@Ag_(14)(Tab)_(12)-(C_(5)H_(4)NCl)_(12)](PF_(6))_(13)(Cl@Ag_(14))and[Cl_(3)@Ag_(24)(Tab)_(20)(C_(5)H_(4)NCl)_(11)]Cl(PF_(6))_(20)(Cl_(3)@Ag_(24))(Tab=4-(trimethylammonio)benzenethiolate,C_(5)H_(4)NCl=3-chloropyridine)were obtained successfully.Notably,the number of chloride ions encapsulated inside the Ag-S shell could be regulated by the slow dissolution of almost insoluble KCl at various temperatures.The inclusion of additional core chloride ions results in the expansion of the surrounding Ag-S shell.This article provides a promising synthetic approach for controlling the number of Ag atoms that form a shell around the anionic core,in addition to offering a potential pathway for the introduction of other inorganic anions into silver clusters.More broadly,through the use of related ligands,the synthetic strategy offers scope for generating new families of silver thiolate clusters of varying size and composition.
基金supported by the National Natural Science Foundation of China(21871196,21773163,21531006)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry(KF2021005)+1 种基金Collaborative Innovation Center of Suzhou Nano Science and Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Project of Scientific and Technologic Infrastructure of Suzhou(SZS201905).
文摘Two atom-precise silver nanoclusters[Ag_(25)Cl_2(Tab)_(14)(Ph COO)_(11)(DMF)_4](PF_6)_(12)(Ag_(25),DMF=N,N-dimethylformamide)and[Ag_(26)Cl_2(Tab)_(14)(Ph COO)_(13)(DMAc)_4](PF_6)_(11)(Ag_(26),DMAc=N,N-dimethylacetamide)were synthesized based on the electrically neutral thiolate protective ligand,4-(trimethylammonio)benzenethiolate(Tab).The weak Ag–S interaction in Tab-protected silver nanoclusters allows to insert or leave a single silver atom in the Ag–S skeleton through solvent-trigger core fragmentation and re-arrangement,thereby realizing the reversible conversion of Ag_(25)and Ag_(26)for the first time.
基金Project supported by the National Natural Science Foundation of China.
文摘 [Co3(1,2-S2C6H4)3(PPh3)3][CoBr3(DMF)].sol (1, sol=CHCl3,O(C2H5)2,H2O) was obtained from the reaction of CoBr(PPh3)3 with Na2(S2C6H4) in chloroform. The Co3 core in the cation of 1 exhibits a metal-metal bonded isosceles triangle, in which the two longer Co-Co bonds are both bridged by S2C6H4 ligands on two sides of the triangle plane respectively, while the bottom short Co-Co bond is bridged by the third bidentate S2C6H4 ligand. A series of polynu-clear cobalt cluster compounds with phosphine, thiolate and/or sulphur ligands were prepared by low oxidation state Co+ with thiolates in organic solvents. These tri-, tetra-, hexa-, heptanuclear cluster compounds 1-8 with various types of crystal structures can be viewed as the condensed polynuclear cobalt complexes that the cobalt atom frameworks with sulphur bridged were built through the small triangular units of [Co3S3nL3] (n=1,2) with or without [CoL] (L=PR3, Br, Cl, 5-C5H5) fragments.
基金This work was supported by the National Natural Science Foundation of China (No. 20572014)
文摘（C5H4SiMe2^tBu）2Ln^nBu reacted with 1 equiv, of elemental sulfur in toluene at ambient temperature to yield the corresponding lanthanocene thiolates [（C5H4SiMe2^tBu）2Ln（μ-S^nBu）]2 （Ln = Y （1）, Er （2））. Complexes 1 and 2 have been characterized by elemental analysis, IR, mass spectroscopy and X-ray single-crystal diffraction analysis. Both complexes are of monoclinic with space group P21/c, formula C52H94S2Si4Y2 1 （C52H94S2Si4Er2 2） Mr = 1073.57 （1230.27）, a = 8.495（2） （8.41（2））, b = 26.913（8） （26.67（7））, c = 13.756（4） （13.68（4）） A, α = 90（90）, β = 101.184（5） （101.57（4））, γ = 90 （90）°, V= 3085.1（15） （3007（14）） A^3, Dc = 1.156 （1.359） g·cm^-3, Z= 2 （2）, F（000） = 1144 （1260）, μ = 2.046 （2.951） cm^-1, R = 0.0687 （0.0749） and wR = 0.1306 （0.1507） for observed reflections with I 〉 2σ（I）. X-ray structures of 1 and 2 definitively prove that only one sulfur atom is inserted into the Ln-C（^nBu） bond, forming a thiolate ligand.
基金supported by the 973 Program (2007CB815301)the National Natural Science Foundation of China (21073192,20733003 and 20871114)+1 种基金the Science Foundation of CAS (KJCX2-YW-H20)Fujian Province (2009HZ0006-1,2006L2005)
文摘A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni（II） atom and the two silver（I） atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni（edt）2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581（11）,b = 12.239（9）,c = 22.316（17） ,β = 103.08（2）o,V = 3613（5） 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F（000） = 1604,T = 293（2） K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ（I）.
基金supported by the National Natural Science Foundation of China(Nos.21231003 and 21203195)
文摘Two diiron dithiolate complexes [Fe2（CO）6（1,8-S2-2-CH2OOCPhC（10）H5）] 1 and[Fe2（CO）6（1,8-S2-2-CH2OOCPh-4-NO2C（10）H5）]2 were synthesized in high yield. The complexes have been confirmed by single-crystal X-ray diffraction and characterized by IR, UV-Vis, ^1H NMR spectroscopy and cyclic voltammetry. They contain a butterfly Fe2S2 core with the Fe1–Fe2 distances of 2.5237（7）A in 1 and 2.5125（12）A in 2, falling in the normal range of Fe–Fe bond length（2.49 - 2.57 A）. The cyclic voltammetry has been used to investigate the electrochemical properties and the electrocatalytic proton reduction for 1 and 2. The complexes display reduction peaks at –1.074 V, –1.535 V（1） and –0.869 V, –1.247 V（2） vs. Fc/Fc^＋, respectively. With using p-Ts OH acid of different concentration, the reduction peak of complex 2 grows non-linear; on the contrary, that of complex 1 is linear with the addition of the acid. Cyclic voltammetry revealed the two complexes are good catalysts in the CH3CN/NBu4PF6 solution.
基金Project supported by the National Natural Science Foundation of China, and the NSF of Academia Sinica and of Fujian Province.
文摘Complex Fe_3(bdt)_3(PBu_3~n)_3 was synthesized in the presence of PBu_3~n and the structural regularities in a series of transition metal complexes containing bdtH_2 ligand were summarized. The title complex crystallizes in the triclinic space group P-, Mr=1195.19, cell parameters: a=13.283(3), b=20.115(5), c=13.156(3), (?)=90.33(2), β= 116.47 (1), γ=92.19(2)°, V=3143.5(2.7)~3, Z=2, d_c=1.26g/cm^3. The structure was solved by direct methods from 4122 unique reflections with I>4σ(I) and reached the final convergence factor of R(Rw) = 0.053 (0.060). The complex exhibits strong paramagnetism.
基金supported by the National Natural Science Foundation of China (20771003)
文摘The title complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817（2）,b = 14.3889（2）,c = 15.2136（2） ,α = 71.018（1）,β = 74.911（1）,γ = 85.146（1）°,V = 2214.86（6） 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ（MoKα） = 0.616 mm-1,F（000） = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I 2σ（I） and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH（CO）（PPh3）2（4-ClPhNHCS2）] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824（8）,2.3495（8） and 1.71（2）,respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.
基金Project supported by the National Natural Science Foundation of China （No. 20271036）, the Natural Science Foundation of Jiangsu Province of China （No. BK2004205） and the Key Laboratory of 0rganic Synthesis of Jiangsu Province of China （No. JSK001）.
文摘Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.
文摘The insertion reaction of phenyl isothiocyanate into the Ln S bond was studied. Phenyl isothiocyanate reacted with [(CH 3C 5H 4) 2Sm(SPh)(THF)] 2 to give the title complex, (CH 3C 5H 4) 2Sm[SC(SPh)NPh](THF), in good yield, which was characterized by elemental analyses, IR, 1H NMR and X ray structural determination. The crystal structure analysis of complex shows that samarium atom is coordinated by two CH 3C 5H 4 groups, one O atom of THF, and N and S atoms from the SC(SPh)NPh ligand to form a distorted trigonal bipyramidal geometry.
基金The project was supported by the Air Force Office of Scientific Research (FA9550-15-1-0154) and the U.S. National Science Foundation (DMREF-0903225).
文摘Recent progress in the research of atomically-precise metal nanoclusters has identified a series of exceptionally stable nanoclusters with specific chemical compositions. Structural determination on such "magic size" nanoclusters revealed a variety of unique structures such as decahedron, icosahedron, as well as hexagonal close packing(hcp) and body-centered cubic(bcc) packing arrangements in gold nanoclusters, which are largely different from the face-centered cubic(fcc) structure in conventional gold nanoparticles. The characteristic geometrical structures enable the nanoclusters to exhibit interesting properties, and these properties are in close correlation with their atomic structures according to the recent studies. Experimental and theoretical analyses have been applied in the structural identification aiming to clarify the universal principle in the structural evolution of nanoclusters. In this mini-review, we summarize recent studies on periodic structural evolution of fcc-based gold nanoclusters protected by thiolates. A series of nanoclusters exhibit one-dimensional growth along the [001] direction in a layer-by-layer manner from Au_(23)(TBBT)_(20) to Au_(36)(TBBT)_(24),Au_(44)(TBBT)_(28), and to Au_(52)(TBBT)_(32)(TBBT: 4-tert-butylbenzenethiolate). The optical properties of these nanoclusters also evolve periodically based on steady-state and ultrafast spectroscopy. In addition, two-dimensional growth from Au_(44)(TBBT)_(28) toward both [100] and [010] directions leads to the Au_(92)(TBBT)_(44) nanocluster, and the recently reported Au_(52)(PET)_(32)(PET: 2-phenylethanethiol) also follows this growth pattern with partial removal of the layer. Theoretical predictions of relevant fcc nanoclusters include Au_(60)(SCH_3)_(36), Au_(68)(SCH_3)_(40), Au_(76)(SCH_3)_(44), etc, for the continuation of 1 D growth pattern, as well as Au_(68)(SR)_(38)mediating the 2 D growth pattern from Au_(44)(TBBT)_(28) to Au_(92)(TBBT)_(44). Overall, this mini-review provides guidelines on the rules of structural evolution o
文摘We reported the synthesis ofAul3o（SPh-Br）50（Br-Ph-SH=4-bromothiophenol） nanocluster with high purity and high yield via ＂size focusing＂ and ＂ligand exchange＂ processes. The time of synthetic process was significantly reduced compared with previous synthetic routine. AU130（SPh-Br）50 was determined by UV-Vis absorption spectros- copy and matrix-assisted laser desorption ionization（MALDI） mass spectroscopy. Thermo-gravimetric analysis （TGA） and size-exclusion chromatogram（SEC） analyses confirmed the purity of AU130（SPh-Br）50. The yield of gold nanoc- lusters was 20%（based on HAuCl4）.
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).
