The structure and binding energy of copper clusters of the size range 70 to 150 were studied by using the embeddedatom method. The stability of the structure of the clusters was studied by calculating the average bind...The structure and binding energy of copper clusters of the size range 70 to 150 were studied by using the embeddedatom method. The stability of the structure of the clusters was studied by calculating the average binding energy per atom, first difference energy and second difference energy of copper cluster. Most of the copper clusters of the size n=70-150 adopt an icosahedral structure. The results show that the trends are in agreement with theoretic prediction for copper clusters. The most stable structures for copper clusters are found at n=77, 90, 95, 131, 139.展开更多
The melting and freezing processes of CUN （N =180, 256, 360, 408, 500, 628 and 736） nanoclnsters are simulated by using micro-canonical molecular dynamics simulation technique, The potential energies and the heat ca...The melting and freezing processes of CUN （N =180, 256, 360, 408, 500, 628 and 736） nanoclnsters are simulated by using micro-canonical molecular dynamics simulation technique, The potential energies and the heat capacities as a function of temperature are obtained. The results reveal that the melting and freezing points increase almost linearly with the atom number in the cluster increasing. All copper nanoclusters have negative heat capacity around the melting and freezing points, and hysteresis effect in the melting/freezing transition is derived in CUN nanoclusters for the first time.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
A systematic study on the structures and electronic properties of copper clusters has been performed using the density functional theory. In the calculation, there are many isomers near the ground state for small copp...A systematic study on the structures and electronic properties of copper clusters has been performed using the density functional theory. In the calculation, there are many isomers near the ground state for small copper clusters. Our results show that the three-dimensional isomers of copper clusters start from Cu7 cluster and then show a tendency to form more compact structures. The results of the formation energy and the second derivative of binding energy with duster size show that besides N = 8, N =11 is also a magic number. Furthermore, it is the first time to find that the ground state of 11-atom clusters is a biplanar structure as same as the 13-atom cluster. The clear odd-even alternation as cluster size for the formation energy indicates the stability of electronic close shell existed in the range studied.展开更多
Three crystal architectures, including one organic compound of benzoyl peroxide（Ⅰ） and two clusters of tri-iron（Ⅲ） and bi-cupper（Ⅱ） with benzoic ligands（2 and 3）, were self-assembled by an in situ redox way...Three crystal architectures, including one organic compound of benzoyl peroxide（Ⅰ） and two clusters of tri-iron（Ⅲ） and bi-cupper（Ⅱ） with benzoic ligands（2 and 3）, were self-assembled by an in situ redox way of benzoyl peroxide oxidants reacting with Mo, Fe and Cu powders, respectively. X-ray crystallographic results show that both the asymmetry tri-iron（Ⅲ） cluster and the benzoylperoxide crystal architecture（2 and 1） with complicated 3D networks were constructed by intermolecular hydrogen-bonding interactions. Contrarily, the symmetrical bi-copper（Ⅱ） cluster crystal architecture（3）, only with π-π stacking between paralleled phenyl groups and without any intermolecular hydrogen-bonding interactions, only presented an 1D zigzag chain along the a-axis.展开更多
The soft deposition of Cu clusters on a Si （001） surface was studied by molecular dynamics simulations. The embedded atom method, the Stillinger-Weber and the Lennar-Jones potentials were used to describe the intera...The soft deposition of Cu clusters on a Si （001） surface was studied by molecular dynamics simulations. The embedded atom method, the Stillinger-Weber and the Lennar-Jones potentials were used to describe the interactions between the cluster atoms, between the substrate atoms, and between the cluster and the substrate atoms, respectively. The Cu13, Cu55, and Cu147 clusters were investigated at different substrate temperatures. We found that the substrate temperature had a significant effect on the Cn147 cluster. For smaller Cu13 and Cu55 clusters, the substrate temperature in the range of study appeared to have little effect on the mean center-of-mass height. The clusters showed better degrees of epitaxy at 800 K. With the same substrate temperature, the Cu55 cluster demonstrated the highest degree of epitaxy, followed by Cu147 and then Cu13 clusters. In addition, the Cu55 cluster showed the lowest mean center-of-mass height. These results suggested that the Cu55 cluster is a better choice for the thin-film formation among the clusters considered. Our studies may provide insight into the formation of desired Cu thin films on a Si substrate.展开更多
The red chunk title compound [Cu4(S5)2(4-Mepy) 4]?4-Mepy) was obtained by the reaction of copper powder with sulfur powder, potassium sulfide and excess 4-methylpyridine at ambient temperature and normal atmosphere. I...The red chunk title compound [Cu4(S5)2(4-Mepy) 4]?4-Mepy) was obtained by the reaction of copper powder with sulfur powder, potassium sulfide and excess 4-methylpyridine at ambient temperature and normal atmosphere. Its structure was determined by single-crystal X-ray diffraction analysis, and the crystal data for the compound: triclinic, P , a = 9.7442(2), b = 14.124(3), c = 15.410 (3) ? ?= 98.96(3), ?= 93.82(3), ?= 94.08(3)? V = 2083.7(7) ?3, Z = 2, Dc = 1.66 g/cm3, (MoK? = 1.31mm-1, F(000) = 1052,C30H35N5S10Cu4,Mr = 1040.45. The structure was refined to R = 0.0393 and wR = 0.1158 for 9281 independent reflections. The title crystal consists of a neutral complex molecule [Cu4(S5)2(4-CH3C5H4N)4] and a 4-methylpyridine solvent molecule. In the neutral complex, the four Cu atoms are in a distorted tetrahedral arrangement and the nonbonding Cu…Cu distances in the copper tetrahedron range from 3.1414 to 3.8488 , and the CuS bond lengths vary from 2.2839 to 2.3670 ?展开更多
We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH） mechan...We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH） mechanisms, respectively. According to these two main reaction mechanisms, we have obtained five reaction pathways for the first CO oxidation（denoted as RER1,RER2, RLH1, RLH2 and RLH3, respectively）： RER1 is COgas ＋ O2（ads） → O（ads） ＋ CO2（gas）; RER2 is COgas ＋ O2（ads） → CO3（ads） → O（ads） ＋ CO2（gas）; RLH1 refers to CO（ads） ＋ O2（ads） → O（ads） ＋ CO2（gas）; RLH2 refers to CO（ads） ＋ O2（ads） → OOCO（ads） → O（ads） ＋ CO2（gas） and RLH3 refers to O2（ads） ＋ CO（ads）→ O（ads） ＋ O（ads） ＋ CO（ads） → O（ads） ＋ CO2（gas）. These pathways have low energy barriers and are strongly exothermic, suggesting the Cu13 cluster is very favorable catalyst for the first CO oxidation. However, there are higher energy barriers of 99. 8 and 45.4 kJ/mol in the process of producing and decomposing intermediates along the RLH2 and RER2, indicating that RER1, RLH1 and RLH3 are superior pathways with lower energy barriers, especially the RER1 channel. Thereafter, the second CO is more prone to react with the remaining oxygen atom on Cu13 along the ER channel in comparison with the LH pathway, in which the moderate barrier is 70.0 kJ/mol and it is exothermic by 59.6 kJ/mol. Furthermore, the interaction between the absorbate and cluster is analyzed by electronic analysis to gain insights into high activity of the copper cluster.展开更多
The title compound [Cu(dtp) PPh3]2 (dtp=S2,P(OEt)2) was prepared by heating the mononuclear compound Cu(dtp)(PPh3)2 in CH3CN solution.It crystallizes in the triclinic space group P1 with parameters a=9.71 6(5),b=11.02...The title compound [Cu(dtp) PPh3]2 (dtp=S2,P(OEt)2) was prepared by heating the mononuclear compound Cu(dtp)(PPh3)2 in CH3CN solution.It crystallizes in the triclinic space group P1 with parameters a=9.71 6(5),b=11.026(5),c=12.475(4) A.α=78.16(3)°,β=102. 64(4), γ=114.34(4)°,V=1178(1)A 3,Z=1,Dc=1.44 g/cm3,MoKα(λ=0.71069 A) μ=12. 48cm-1,F(000)=528.Final R=0.041.Rω= 0. 052 for 3653 unique intensity data(I≥3σ(I)).The molecule of the title compound can be viewed as a centrosymmetric dimer with two[Cu(dtp)(PPh3)] units,which are bridged by two S atoms belonging to the dtp ligands.The exact planar[Cu2S2] core and two[CuS2P] four-membered rings form a chair conformation.The Cu…Cu distance is 2.991(5) A.展开更多
In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±...In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±1 allowing transition and △M=2 forbiding transition are shown in EPR spectra. The experimental data are consistent with the calculated results by the leastsquares fitting prograrn in three principal planes of g and D tensors. The spin Hamiltonian parameters are as follows: gx=2. 1482, gy=2. 0529 ,gz=2. 3905, D= 0. 348 cm￣(-1) and E =0. 01 cm-1. The diagrams of the energy levels have been obtained when the magnetic field is oriented to three principal axes. The polycrystal EPR spectra have been measured at room temperature and 77K, respectively.and the parameters of these spectra are given (g∥= 2. 094, g⊥= 2. 425, D= 0. 37 cm-1,E=0). The parameter of the isotropic magnetic exchange interaction J=-254cm-1 is determined, and that of the anisotropic magnetic exchange J1=-153 cm-1 is calculated. The average magnetic susceptibility of the polycrystal sample χ= 1. 39 ×10-6 (c. g. s) has been measured by Faraday powder method. Thus the average magnetic mornent μ=1. 43 B. M. can be calculated. It is shown that the exchange interactions between the metal ions of the binuclear copper(Ⅱ) cluster compound are confirmed antiferromagnetic In nature.展开更多
The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the ...The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2（dmpzm）2]·DMF（2·DMF）.Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2（MeCN）0.5 crystallizes in triclinic,space group P1-with a = 11.4552（5）,b = 11.6735（3）,c = 16.2278（9） ,α = 99.537（9）,β = 101.986（2）,γ = 118.464（13）o,V = 1775.5（3）3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193（2） K,C24H35Cu3IN9OS3W,Mr = 1063.22,F（000） = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145（4）,b = 11.464（2）,c = 7.7370（15） ,V = 1964.2（6）3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193（2） K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F（000） = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2（MeCN）0.5 consists of one CuI and two [Cu（dmpzm）]＋ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.展开更多
A novel 3D hetero-nuclear framework,namely{[K_(5)Na_(6)Cu^(Ⅱ)_(5)(CH_(3)COO)_(20)(CH_(3)CN)]Cl}_(n)(1),was obtained by hydrothermal reaction.Triple metal centers(including sodium/potassium or/and copper)were coordina...A novel 3D hetero-nuclear framework,namely{[K_(5)Na_(6)Cu^(Ⅱ)_(5)(CH_(3)COO)_(20)(CH_(3)CN)]Cl}_(n)(1),was obtained by hydrothermal reaction.Triple metal centers(including sodium/potassium or/and copper)were coordinated to acetate anions in such two heteronuclear clusters,respectively.Moreover,nine kinds of binding modes for acetate anions were illustrated in polymer 1,with the first reported pentadentate coordination mode for acetate ligand.展开更多
In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±...In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±1 allowing transition and △M=2 forbiding transition are shown in EPR spectra. The experimental data are consistent with the calculated results by the leastsquares fitting prograrn in three principal planes of g and D tensors. The spin Hamiltonian parameters are as follows: gx=2. 1482, gy=2. 0529 ,gz=2. 3905, D= 0. 348 cm￣(-1) and E =0. 01 cm-1. The diagrams of the energy levels have been obtained when the magnetic field is oriented to three principal axes. The polycrystal EPR spectra have been measured at room temperature and 77K, respectively.and the parameters of these spectra are given (g∥= 2. 094, g⊥= 2. 425, D= 0. 37 cm-1,E=0). The parameter of the isotropic magnetic exchange interaction J=-254cm-1 is determined, and that of the anisotropic magnetic exchange J1=-153 cm-1 is calculated. The average magnetic susceptibility of the polycrystal sample χ= 1. 39 ×10-6 (c. g. s) has been measured by Faraday powder method. Thus the average magnetic mornent μ=1. 43 B. M. can be calculated. It is shown that the exchange interactions between the metal ions of the binuclear copper(Ⅱ) cluster compound are confirmed antiferromagnetic In nature.展开更多
The major impediment to the additional industrialization of water splitting is the high cost of the co-catalyst made of noble metals and the sacrificial reagent. A binary photocatalytic system, consisting of B-doped g...The major impediment to the additional industrialization of water splitting is the high cost of the co-catalyst made of noble metals and the sacrificial reagent. A binary photocatalytic system, consisting of B-doped g-C_(3)N_(4) nanosheets(Cu_(20)@BCN-X) and atomically accurate copper clusters, is designed in this study. The copper clusters serve as co-catalysts for H_(2) evolution and exhibit Pt-like activity, whereas the nanosheets serve as carriers and semiconductor components for O_(2) evolution. Such binary system, created using simple techniques, demonstrates hydrogen bonding interactions that promote synergistic effects and efficient binding and charge transfer across the interface between the two components. Band position manipulation of carbon nitride nanosheets demonstrates a Z-scheme charge transfer mechanism between the nanosheets and copper clusters. This photocatalytic system can accomplish the photocatalytic overall water splitting process(259.9 μmol g^(-1)h^(-1)of H_(2) and 129.4 μmol g^(-1)h^(-1)of O_(2)) without using sacrificial agents or noble metal co-catalysts. This work lays the foundation for the design of overall water splitting catalysts by precisely manipulating the energy levels, and it also paves the way for commercialized photocatalytic catalysts that do not require noble metals or sacrificial chemicals.展开更多
The weakness of visible and near-infrared light penetration depth limits the application of photodynamic therapy(PDT)in deep-seated tumors.Based on the high penetrability of X-rays,X-ray-induced PDT(X-PDT)is a promisi...The weakness of visible and near-infrared light penetration depth limits the application of photodynamic therapy(PDT)in deep-seated tumors.Based on the high penetrability of X-rays,X-ray-induced PDT(X-PDT)is a promising new method for treating deep-seated tumors.However,it requires the development of suitable X-ray-induced sensitizers that could employ X-ray energy to produce reactive oxygen species(ROS)efficiently.In this study,a novel X-rayinduced sensitizer(NanoSRF)was developed through a microemulsion method,in which copper iodine cluster compound Cu_(2)I_(2)(tpp)2(2,5-dm-pz)(CIP)and rose bengal(RB)worked as scintillator and photosensitizer,respectively.CIP was synthesized by a simple mechanical grinding method,and subsequently folic acid(FA)-modified albumin was introduced to enable its alliance with RB.NanoSRF exhibited excellent dispersion stability and generated a large amount of ROS under X-ray irradiation.The results of in vitro studies demonstrated its high selectivity for FA receptor-positive cancer cells.Following systemic administration,NanoSRF accumulated in H22 tumors of xenograft-bearing mice,and Xray irradiation(5.46 Gy)induced a significant inhibition rate of 96.7%in tumor growth.This study pioneers the use of copper iodide cluster as a scintillator in X-PDT,presenting new possibilities for designing scintillators with exceptional X-ray absorption and efficient X-PDT capabilities.展开更多
Chiral hybrid metal halides with high photoluminescence quantum yield(PLQY)and superior dissymmetry factor(g_(lum))are promising candidates for circularly polarized luminescence(CPL)emitting sources.However,it is a gr...Chiral hybrid metal halides with high photoluminescence quantum yield(PLQY)and superior dissymmetry factor(g_(lum))are promising candidates for circularly polarized luminescence(CPL)emitting sources.However,it is a great challenge to achieve both high g_(lum)and large PLQY.Here,we report a new supramolecular strategy to fabricate chiral hybrid Cu(Ⅰ)-halides with nearunity quantum yields and intense CPL emissions.The dissymmetry factor can be dramatically modulated by tuning the hostguest complexations.Attributing to the chirality and variable conformations of the host-guest complexes,a series of chiral[G@L^(R/S)]_(2)Cu_(4)I_(6)have been prepared.The incorporation of different cations within the chiral L^(R/S)hosts leads to variations of packing modes along the c-axis and different extent of distortions in the[Cu_(4)I_(6)]_(2)-polyhedra.Among them,[H_(3)O@L^(R/S)]+cations are stacked based on Van der Waals interactions and hierarchically self-assemble into a right/left-handed helix in[H_(3)O@L^(R/S)]_(2)Cu_(4)I_(6),which results in a high g_(lum)of-7×10^(-3)and a large PLQY of 96.92%.Notably,[G@L^(R/S)]_(2)Cu_(4)I_(6)shows promising applications in single-component white light emitting diodes(WLEDs),exhibiting a maximum dissymmetry factor of-1.2×10^(-3).The effective host-guest complexation and oriented hierarchical self-assembly provide an effective strategy for the development of high-performance CPL materials.展开更多
Sensitivity to structure and composition is very challenging to establish in nanocatalysis due to inadequate definition of structures that are very close in composition.We synthesized a pair of atomically precise copp...Sensitivity to structure and composition is very challenging to establish in nanocatalysis due to inadequate definition of structures that are very close in composition.We synthesized a pair of atomically precise copper clusters that are very close in composition,[Cu_(20)H_(9)(Tf-dpf)_(10)]·BF4(Cu_(20)H_(9))and[Cu_(20)H_(8)(Tf-dpf)_(10)]·(BF_(4))_(2)(Cu_(20)H_(8)),by using a pyridyl-functionalized flexible amidinate ligand,N,N′-di(5-trifluoromethyl-2-pyridyl)formamidinate.The one-hydride difference in their composition leads to significant variation in geometric and electronic structures and,consequently,distinctly different optical and catalytic properties.Cu_(20)H_(8)exhibits 25 times higher catalytic activity than Cu_(20)H_(9)(96.7%vs 3.7%in yield)in the selective hydrogenation of anα,β-unsaturated aldehyde(cinnamaldehyde)to saturated aldehyde(3-phenylpropanal).Electrospray ionization mass spectrometry combined with density functional theory calculations reveal that the greater ease of dissociation of one Tf-dpf ligand compared to Cu_(20)H_(8)is the key to its higher activity.This work demonstrates a clear case of structure and composition sensitivity in nanocatalysis and that one hydride,out of∼330 atoms in the nanoclusters,can make a huge difference in the catalytic activity.These insights will be useful in the design and synthesis of atomically precise nanocatalysts.展开更多
Stimuli-responsive luminescent materials have attracted significant attention in the development of smart photoactive materials for both fundamental research and technological applications.In this work,a new copper io...Stimuli-responsive luminescent materials have attracted significant attention in the development of smart photoactive materials for both fundamental research and technological applications.In this work,a new copper iodide cluster(1)with aggregationinduced emission(AIE)characteristic,was obtained combining Cu_(4)I_(4) core with rhodamine B derivative ligand.1 has reversible and distinct multi-stimuli-responsive luminescence for external temperature,volatile organic compound,and mechanical force.Significantly,1 exhibited unusual large blue shift(84 nm)after being ground,which originated from the change of intermolecular interactions.Moreover,1 exhibits high oxygen quenching efficiency for 82.2% at 1 bar.Mechanistic studies showed that the multi-stimuli-responsive luminescence properties of 1 can be attributed to the regulation of cluster-centered luminescence process,metal-to-ligand charge transfer process,halide-to-metal charge transfer luminescence process and aggregationinduced barrier to oxygen process.This work not only reports an AIE copper iodide cluster,but also provides a new strategy to develop multi-stimuli-responsive luminescence materials.展开更多
A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-cr...A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.展开更多
The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was dete...The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) ? V = 7054.6(8) 3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, m (Mo Ka) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one [(h5-C5Me5)WS3(CuBr)3]22- dianion, one [Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (h5-C5Me5)WS3(CuBr)3 fragments connected by a pair of CuBrCu bridges to form a double incomplete-cubane structure. The range of WCu distance is 2.657(1)~2.677(2) ?in the W2Cu6S6 cluster core.展开更多
基金supported by the National Natural Science Foundation of China (Grant No 10375028)
文摘The structure and binding energy of copper clusters of the size range 70 to 150 were studied by using the embeddedatom method. The stability of the structure of the clusters was studied by calculating the average binding energy per atom, first difference energy and second difference energy of copper cluster. Most of the copper clusters of the size n=70-150 adopt an icosahedral structure. The results show that the trends are in agreement with theoretic prediction for copper clusters. The most stable structures for copper clusters are found at n=77, 90, 95, 131, 139.
文摘The melting and freezing processes of CUN （N =180, 256, 360, 408, 500, 628 and 736） nanoclnsters are simulated by using micro-canonical molecular dynamics simulation technique, The potential energies and the heat capacities as a function of temperature are obtained. The results reveal that the melting and freezing points increase almost linearly with the atom number in the cluster increasing. All copper nanoclusters have negative heat capacity around the melting and freezing points, and hysteresis effect in the melting/freezing transition is derived in CUN nanoclusters for the first time.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
文摘A systematic study on the structures and electronic properties of copper clusters has been performed using the density functional theory. In the calculation, there are many isomers near the ground state for small copper clusters. Our results show that the three-dimensional isomers of copper clusters start from Cu7 cluster and then show a tendency to form more compact structures. The results of the formation energy and the second derivative of binding energy with duster size show that besides N = 8, N =11 is also a magic number. Furthermore, it is the first time to find that the ground state of 11-atom clusters is a biplanar structure as same as the 13-atom cluster. The clear odd-even alternation as cluster size for the formation energy indicates the stability of electronic close shell existed in the range studied.
基金Supported by the National Natural Science Foundation of China(No.20771073)
文摘Three crystal architectures, including one organic compound of benzoyl peroxide（Ⅰ） and two clusters of tri-iron（Ⅲ） and bi-cupper（Ⅱ） with benzoic ligands（2 and 3）, were self-assembled by an in situ redox way of benzoyl peroxide oxidants reacting with Mo, Fe and Cu powders, respectively. X-ray crystallographic results show that both the asymmetry tri-iron（Ⅲ） cluster and the benzoylperoxide crystal architecture（2 and 1） with complicated 3D networks were constructed by intermolecular hydrogen-bonding interactions. Contrarily, the symmetrical bi-copper（Ⅱ） cluster crystal architecture（3）, only with π-π stacking between paralleled phenyl groups and without any intermolecular hydrogen-bonding interactions, only presented an 1D zigzag chain along the a-axis.
基金Project supported by the National Natural Science Foundation of China (Grant No. 10375028)the US National Science Foundation Award (Grant No. CMMI-0700048)
文摘The soft deposition of Cu clusters on a Si （001） surface was studied by molecular dynamics simulations. The embedded atom method, the Stillinger-Weber and the Lennar-Jones potentials were used to describe the interactions between the cluster atoms, between the substrate atoms, and between the cluster and the substrate atoms, respectively. The Cu13, Cu55, and Cu147 clusters were investigated at different substrate temperatures. We found that the substrate temperature had a significant effect on the Cn147 cluster. For smaller Cu13 and Cu55 clusters, the substrate temperature in the range of study appeared to have little effect on the mean center-of-mass height. The clusters showed better degrees of epitaxy at 800 K. With the same substrate temperature, the Cu55 cluster demonstrated the highest degree of epitaxy, followed by Cu147 and then Cu13 clusters. In addition, the Cu55 cluster showed the lowest mean center-of-mass height. These results suggested that the Cu55 cluster is a better choice for the thin-film formation among the clusters considered. Our studies may provide insight into the formation of desired Cu thin films on a Si substrate.
基金Supported by the Natural Science Foundation of Fujian Education Committee(JB01045)
文摘The red chunk title compound [Cu4(S5)2(4-Mepy) 4]?4-Mepy) was obtained by the reaction of copper powder with sulfur powder, potassium sulfide and excess 4-methylpyridine at ambient temperature and normal atmosphere. Its structure was determined by single-crystal X-ray diffraction analysis, and the crystal data for the compound: triclinic, P , a = 9.7442(2), b = 14.124(3), c = 15.410 (3) ? ?= 98.96(3), ?= 93.82(3), ?= 94.08(3)? V = 2083.7(7) ?3, Z = 2, Dc = 1.66 g/cm3, (MoK? = 1.31mm-1, F(000) = 1052,C30H35N5S10Cu4,Mr = 1040.45. The structure was refined to R = 0.0393 and wR = 0.1158 for 9281 independent reflections. The title crystal consists of a neutral complex molecule [Cu4(S5)2(4-CH3C5H4N)4] and a 4-methylpyridine solvent molecule. In the neutral complex, the four Cu atoms are in a distorted tetrahedral arrangement and the nonbonding Cu…Cu distances in the copper tetrahedron range from 3.1414 to 3.8488 , and the CuS bond lengths vary from 2.2839 to 2.3670 ?
基金supported by the National Natural Science Foundation of China(Nos.51574090 and 21773030)Natural Science Foundation of Fujian Province(2017J01409)
文摘We have studied the reaction mechanism of CO oxidation on the Cu13 cluster via density functional theory. There are two main reaction pathways to be considered： Eley-Rideal（ER） and Langmuir-Hinshelwood（LH） mechanisms, respectively. According to these two main reaction mechanisms, we have obtained five reaction pathways for the first CO oxidation（denoted as RER1,RER2, RLH1, RLH2 and RLH3, respectively）： RER1 is COgas ＋ O2（ads） → O（ads） ＋ CO2（gas）; RER2 is COgas ＋ O2（ads） → CO3（ads） → O（ads） ＋ CO2（gas）; RLH1 refers to CO（ads） ＋ O2（ads） → O（ads） ＋ CO2（gas）; RLH2 refers to CO（ads） ＋ O2（ads） → OOCO（ads） → O（ads） ＋ CO2（gas） and RLH3 refers to O2（ads） ＋ CO（ads）→ O（ads） ＋ O（ads） ＋ CO（ads） → O（ads） ＋ CO2（gas）. These pathways have low energy barriers and are strongly exothermic, suggesting the Cu13 cluster is very favorable catalyst for the first CO oxidation. However, there are higher energy barriers of 99. 8 and 45.4 kJ/mol in the process of producing and decomposing intermediates along the RLH2 and RER2, indicating that RER1, RLH1 and RLH3 are superior pathways with lower energy barriers, especially the RER1 channel. Thereafter, the second CO is more prone to react with the remaining oxygen atom on Cu13 along the ER channel in comparison with the LH pathway, in which the moderate barrier is 70.0 kJ/mol and it is exothermic by 59.6 kJ/mol. Furthermore, the interaction between the absorbate and cluster is analyzed by electronic analysis to gain insights into high activity of the copper cluster.
文摘The title compound [Cu(dtp) PPh3]2 (dtp=S2,P(OEt)2) was prepared by heating the mononuclear compound Cu(dtp)(PPh3)2 in CH3CN solution.It crystallizes in the triclinic space group P1 with parameters a=9.71 6(5),b=11.026(5),c=12.475(4) A.α=78.16(3)°,β=102. 64(4), γ=114.34(4)°,V=1178(1)A 3,Z=1,Dc=1.44 g/cm3,MoKα(λ=0.71069 A) μ=12. 48cm-1,F(000)=528.Final R=0.041.Rω= 0. 052 for 3653 unique intensity data(I≥3σ(I)).The molecule of the title compound can be viewed as a centrosymmetric dimer with two[Cu(dtp)(PPh3)] units,which are bridged by two S atoms belonging to the dtp ligands.The exact planar[Cu2S2] core and two[CuS2P] four-membered rings form a chair conformation.The Cu…Cu distance is 2.991(5) A.
文摘In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±1 allowing transition and △M=2 forbiding transition are shown in EPR spectra. The experimental data are consistent with the calculated results by the leastsquares fitting prograrn in three principal planes of g and D tensors. The spin Hamiltonian parameters are as follows: gx=2. 1482, gy=2. 0529 ,gz=2. 3905, D= 0. 348 cm￣(-1) and E =0. 01 cm-1. The diagrams of the energy levels have been obtained when the magnetic field is oriented to three principal axes. The polycrystal EPR spectra have been measured at room temperature and 77K, respectively.and the parameters of these spectra are given (g∥= 2. 094, g⊥= 2. 425, D= 0. 37 cm-1,E=0). The parameter of the isotropic magnetic exchange interaction J=-254cm-1 is determined, and that of the anisotropic magnetic exchange J1=-153 cm-1 is calculated. The average magnetic susceptibility of the polycrystal sample χ= 1. 39 ×10-6 (c. g. s) has been measured by Faraday powder method. Thus the average magnetic mornent μ=1. 43 B. M. can be calculated. It is shown that the exchange interactions between the metal ions of the binuclear copper(Ⅱ) cluster compound are confirmed antiferromagnetic In nature.
基金Supported by the National Natural Science Foundation of China (No. 20525101,20801038) "Soochow Scholar" Program of Suzhou University
文摘The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2（dmpzm）2]·DMF（2·DMF）.Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2（MeCN）0.5 crystallizes in triclinic,space group P1-with a = 11.4552（5）,b = 11.6735（3）,c = 16.2278（9） ,α = 99.537（9）,β = 101.986（2）,γ = 118.464（13）o,V = 1775.5（3）3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193（2） K,C24H35Cu3IN9OS3W,Mr = 1063.22,F（000） = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145（4）,b = 11.464（2）,c = 7.7370（15） ,V = 1964.2（6）3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193（2） K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F（000） = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2（MeCN）0.5 consists of one CuI and two [Cu（dmpzm）]＋ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.
基金financially supported by the Youth Teachers'Training Foundation of Minnan Science and Technology InstituteYoung and Middle-age academic leader plan of Quanzhou universitythe undergraduate education teaching reform in Fujian province(2017)
文摘A novel 3D hetero-nuclear framework,namely{[K_(5)Na_(6)Cu^(Ⅱ)_(5)(CH_(3)COO)_(20)(CH_(3)CN)]Cl}_(n)(1),was obtained by hydrothermal reaction.Triple metal centers(including sodium/potassium or/and copper)were coordinated to acetate anions in such two heteronuclear clusters,respectively.Moreover,nine kinds of binding modes for acetate anions were illustrated in polymer 1,with the first reported pentadentate coordination mode for acetate ligand.
文摘In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±1 allowing transition and △M=2 forbiding transition are shown in EPR spectra. The experimental data are consistent with the calculated results by the leastsquares fitting prograrn in three principal planes of g and D tensors. The spin Hamiltonian parameters are as follows: gx=2. 1482, gy=2. 0529 ,gz=2. 3905, D= 0. 348 cm￣(-1) and E =0. 01 cm-1. The diagrams of the energy levels have been obtained when the magnetic field is oriented to three principal axes. The polycrystal EPR spectra have been measured at room temperature and 77K, respectively.and the parameters of these spectra are given (g∥= 2. 094, g⊥= 2. 425, D= 0. 37 cm-1,E=0). The parameter of the isotropic magnetic exchange interaction J=-254cm-1 is determined, and that of the anisotropic magnetic exchange J1=-153 cm-1 is calculated. The average magnetic susceptibility of the polycrystal sample χ= 1. 39 ×10-6 (c. g. s) has been measured by Faraday powder method. Thus the average magnetic mornent μ=1. 43 B. M. can be calculated. It is shown that the exchange interactions between the metal ions of the binuclear copper(Ⅱ) cluster compound are confirmed antiferromagnetic In nature.
基金supported by the National Natural Science Foundation of China (21971085)the Natural Science Foundation of Shandong Province (ZR2021MB008)the Jinan City “New University 20” Project (202228113)。
文摘The major impediment to the additional industrialization of water splitting is the high cost of the co-catalyst made of noble metals and the sacrificial reagent. A binary photocatalytic system, consisting of B-doped g-C_(3)N_(4) nanosheets(Cu_(20)@BCN-X) and atomically accurate copper clusters, is designed in this study. The copper clusters serve as co-catalysts for H_(2) evolution and exhibit Pt-like activity, whereas the nanosheets serve as carriers and semiconductor components for O_(2) evolution. Such binary system, created using simple techniques, demonstrates hydrogen bonding interactions that promote synergistic effects and efficient binding and charge transfer across the interface between the two components. Band position manipulation of carbon nitride nanosheets demonstrates a Z-scheme charge transfer mechanism between the nanosheets and copper clusters. This photocatalytic system can accomplish the photocatalytic overall water splitting process(259.9 μmol g^(-1)h^(-1)of H_(2) and 129.4 μmol g^(-1)h^(-1)of O_(2)) without using sacrificial agents or noble metal co-catalysts. This work lays the foundation for the design of overall water splitting catalysts by precisely manipulating the energy levels, and it also paves the way for commercialized photocatalytic catalysts that do not require noble metals or sacrificial chemicals.
基金supported by the National Natural Science Foundation of China(22178065,22078066 and U1705282).
文摘The weakness of visible and near-infrared light penetration depth limits the application of photodynamic therapy(PDT)in deep-seated tumors.Based on the high penetrability of X-rays,X-ray-induced PDT(X-PDT)is a promising new method for treating deep-seated tumors.However,it requires the development of suitable X-ray-induced sensitizers that could employ X-ray energy to produce reactive oxygen species(ROS)efficiently.In this study,a novel X-rayinduced sensitizer(NanoSRF)was developed through a microemulsion method,in which copper iodine cluster compound Cu_(2)I_(2)(tpp)2(2,5-dm-pz)(CIP)and rose bengal(RB)worked as scintillator and photosensitizer,respectively.CIP was synthesized by a simple mechanical grinding method,and subsequently folic acid(FA)-modified albumin was introduced to enable its alliance with RB.NanoSRF exhibited excellent dispersion stability and generated a large amount of ROS under X-ray irradiation.The results of in vitro studies demonstrated its high selectivity for FA receptor-positive cancer cells.Following systemic administration,NanoSRF accumulated in H22 tumors of xenograft-bearing mice,and Xray irradiation(5.46 Gy)induced a significant inhibition rate of 96.7%in tumor growth.This study pioneers the use of copper iodide cluster as a scintillator in X-PDT,presenting new possibilities for designing scintillators with exceptional X-ray absorption and efficient X-PDT capabilities.
基金supported by the Science Foundation of Fujian Province(2021J02016,2023J01528)the National Natural Science Foundation of China(21901245,22171264)。
文摘Chiral hybrid metal halides with high photoluminescence quantum yield(PLQY)and superior dissymmetry factor(g_(lum))are promising candidates for circularly polarized luminescence(CPL)emitting sources.However,it is a great challenge to achieve both high g_(lum)and large PLQY.Here,we report a new supramolecular strategy to fabricate chiral hybrid Cu(Ⅰ)-halides with nearunity quantum yields and intense CPL emissions.The dissymmetry factor can be dramatically modulated by tuning the hostguest complexations.Attributing to the chirality and variable conformations of the host-guest complexes,a series of chiral[G@L^(R/S)]_(2)Cu_(4)I_(6)have been prepared.The incorporation of different cations within the chiral L^(R/S)hosts leads to variations of packing modes along the c-axis and different extent of distortions in the[Cu_(4)I_(6)]_(2)-polyhedra.Among them,[H_(3)O@L^(R/S)]+cations are stacked based on Van der Waals interactions and hierarchically self-assemble into a right/left-handed helix in[H_(3)O@L^(R/S)]_(2)Cu_(4)I_(6),which results in a high g_(lum)of-7×10^(-3)and a large PLQY of 96.92%.Notably,[G@L^(R/S)]_(2)Cu_(4)I_(6)shows promising applications in single-component white light emitting diodes(WLEDs),exhibiting a maximum dissymmetry factor of-1.2×10^(-3).The effective host-guest complexation and oriented hierarchical self-assembly provide an effective strategy for the development of high-performance CPL materials.
基金supported by the National Natural Science Foundation of China(grant nos.91961201 and 21973116)the Beijing Natural Science Foundation(grant no.2234087)the China Postdoctoral Science Foundation(grant nos.2023T160357 and 2022M721797).
文摘Sensitivity to structure and composition is very challenging to establish in nanocatalysis due to inadequate definition of structures that are very close in composition.We synthesized a pair of atomically precise copper clusters that are very close in composition,[Cu_(20)H_(9)(Tf-dpf)_(10)]·BF4(Cu_(20)H_(9))and[Cu_(20)H_(8)(Tf-dpf)_(10)]·(BF_(4))_(2)(Cu_(20)H_(8)),by using a pyridyl-functionalized flexible amidinate ligand,N,N′-di(5-trifluoromethyl-2-pyridyl)formamidinate.The one-hydride difference in their composition leads to significant variation in geometric and electronic structures and,consequently,distinctly different optical and catalytic properties.Cu_(20)H_(8)exhibits 25 times higher catalytic activity than Cu_(20)H_(9)(96.7%vs 3.7%in yield)in the selective hydrogenation of anα,β-unsaturated aldehyde(cinnamaldehyde)to saturated aldehyde(3-phenylpropanal).Electrospray ionization mass spectrometry combined with density functional theory calculations reveal that the greater ease of dissociation of one Tf-dpf ligand compared to Cu_(20)H_(8)is the key to its higher activity.This work demonstrates a clear case of structure and composition sensitivity in nanocatalysis and that one hydride,out of∼330 atoms in the nanoclusters,can make a huge difference in the catalytic activity.These insights will be useful in the design and synthesis of atomically precise nanocatalysts.
基金supported by the National Natural Science Foundation of China(92061201,21825106,22371264,22301283)the Excellent Young Scientist Fundation of Henan Province(202300410374)+1 种基金the Program for Science&Technology Innovation Talents in Universities of Henan Province(22HASTIT002)Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(234000510007)。
文摘Stimuli-responsive luminescent materials have attracted significant attention in the development of smart photoactive materials for both fundamental research and technological applications.In this work,a new copper iodide cluster(1)with aggregationinduced emission(AIE)characteristic,was obtained combining Cu_(4)I_(4) core with rhodamine B derivative ligand.1 has reversible and distinct multi-stimuli-responsive luminescence for external temperature,volatile organic compound,and mechanical force.Significantly,1 exhibited unusual large blue shift(84 nm)after being ground,which originated from the change of intermolecular interactions.Moreover,1 exhibits high oxygen quenching efficiency for 82.2% at 1 bar.Mechanistic studies showed that the multi-stimuli-responsive luminescence properties of 1 can be attributed to the regulation of cluster-centered luminescence process,metal-to-ligand charge transfer process,halide-to-metal charge transfer luminescence process and aggregationinduced barrier to oxygen process.This work not only reports an AIE copper iodide cluster,but also provides a new strategy to develop multi-stimuli-responsive luminescence materials.
基金the Natural Science Foundation of China Fujian Province and Chinese Academy of Sciences.
文摘A new octanuclear VSCu cluster {V2S6Cu6}(PPh3)6(O)22CH2Cl2CH3OH 1 has been prepared by extraction with CH2Cl2 of a solid mixture of (NH4)3VS4, Cu(PPh3)2Cl and NEt4Br, and its structure has been determined by single-crystal X-ray diffraction. Crystallographic data: C111H98Cl4Cu6O3P6S6V2, Mr = 2248.99, triclinic space group P , a = 13.751(6), b = 15.509(4), c = 15.642(5) ? a =114.34(2), b = 98.35(3), g = 110.43(3) , V = 2679.83 3, Z = 1, Dc = 1.538 g/cm3, F(000) = 1262, m (MoKa) = 16.9 cm-1, the final R = 0.079 and Rw = 0.083 for 5504 observed reflections with I > 2s(I). The structural determination shows that the skeleton can be described as a metal-sulfur dodecahedral cage fused by two incomplete cubane-like [VS3Cu3] subunits centrosymmetrically connected by CuS and weak CuCu bonds. The six copper and two vanadium atoms display a slightly distorted cubic array with a m4-S atom on each face of the metal cube. The selected IR, electronic and 51V NMR spectra have also been reported.
基金supported by Suzhou University(XQ109020 and Q4109927)
文摘The reactions of [PPh4][(h5-C5Me5)WS3] with four equiv of CuBr in DMF gave rise to a new cluster salt [Cu(DMF)6][(h5-C5Me5)WS3(CuBr)3]2稥t2O 1. The crystal structure of 1 (C42H76N6O7Br6Cu7S6W2, Mr = 2261.40) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic, space group Pbcm with a = 9.419(1), b = 28.237(1), c = 16.488(3) ? V = 7054.6(8) 3, Z = 4, Dc = 2.129 g/cm3, F(000) = 4332, m (Mo Ka) = 89.46 cm-1 and T = 193 K. With the use of 5746 observed reflections (I > 3.0s(I)), the structure was refined to R = 0.045 and Rw = 0.060. 1 is composed of one [(h5-C5Me5)WS3(CuBr)3]22- dianion, one [Cu(DMF)6]2+ cation and one Et2O solvent molecule. The cluster dianion contains two incomplete-cubane (h5-C5Me5)WS3(CuBr)3 fragments connected by a pair of CuBrCu bridges to form a double incomplete-cubane structure. The range of WCu distance is 2.657(1)~2.677(2) ?in the W2Cu6S6 cluster core.
