The chemical shifts of 1H-NMR of five Fe_3S_3 cluster compounds were assigned. The main chemical shift values are: δ_ CH_3=1.095-1.946, δ_ CH_2=2.882-3\^803, δ_ C_6H_n=7.547-7.172. In comparison with those of...The chemical shifts of 1H-NMR of five Fe_3S_3 cluster compounds were assigned. The main chemical shift values are: δ_ CH_3=1.095-1.946, δ_ CH_2=2.882-3\^803, δ_ C_6H_n=7.547-7.172. In comparison with those of pure (CH_3CH_2)_3N and thiophenol, these values are moved to high position, and the width of these peaks is obviously increased. These characteristics conformed to NMR spectra of paramagnetic compounds and their molecular structures. The paramagnetic property of these compounds was also studied with ESR spectrum. Mass spectra of three compounds were determined. The main fragments were observed, for example, m/z: 130〔(C_2H_5)_4N〕+, 264〔Fe_3S_3〕+, 144〔Fe-S-Fe〕+, 120〔S-Fe-S〕+, 88〔Fe-S〕+, 136〔FeBr〕+, 91〔FeCl〕+ etc. These supported structural characteristics of the anion skeleton and molecules strongly. The possible mechanism of fragmentation was discussed.展开更多
The [Zr6(μ2-Cl)12Cl6H4]3- ion with C4v Symmetry in the title compounds has been calculated by DV-Xα program. The calculated results show that ther is almost no available covalence bonding between zirconium ato...The [Zr6(μ2-Cl)12Cl6H4]3- ion with C4v Symmetry in the title compounds has been calculated by DV-Xα program. The calculated results show that ther is almost no available covalence bonding between zirconium atoms and significant Zr 4d AO compositions in the MOs. but there are much stronger Zr-Cl(bridging) bonding. All analysis results suggest that these compounds would be the cluster with Zr6Cl12 cage linked by Zr-Cl bridging bonding plus six Cl teminal ligands rather than the hexazirconium cluster in view of the chemical bonding.展开更多
A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray...A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.展开更多
By use of self-consistent field Xα scattered-wave (SCF-Xα-SW) method, the electronic structure was calculated for four models of Ti4Al14X (X=Al, Fe, Ni and Cu) clusters. The Ti4Al14X cluster was developed based on L...By use of self-consistent field Xα scattered-wave (SCF-Xα-SW) method, the electronic structure was calculated for four models of Ti4Al14X (X=Al, Fe, Ni and Cu) clusters. The Ti4Al14X cluster was developed based on L12 Al3Ti-base intermetallic compound. The results are presented using the density of states (DOS) and one-electron properties, such as relative binding tendency between the atom and the model cluster, and hybrid bonding tendency between the alloying element and the host atoms. By comparing the four models of Ti4Al14X cluster, the effect of the Fe, Ni or Cu atom on the physical properties of Al3Ti-based L12 intermetallic compounds is analyzed. The results indicate that the addition of the Fe, Ni or Cu atom intensifies the relative binding tendency between Ti atom and Ti4Al14X cluster. It was found that the Fermi level (EF) lies in a maximum in the DOS for Ti4Al14Al cluster; on the contrary, the EF comes near a minimum tn the DOS for Ti4Al14X (X=Fe, Ni and Cu) cluster. Thus the L12 crystal structure for binary Al3Ti alloy is unstable, and the addition of the Fe, Ni or Cu atom to Al3Ti is benefical to stabilize L12 crystal structure. The calculation also shows that the Fe, Ni or Cu atom strengthens the hybrid bonding tendency between the central atom and the host atoms for Ti4Al14X cluster and thereby may lead to the constriction of the lattice of Al3Ti-base intermetallic compounds.展开更多
Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state produced four mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which (1:M=Mo,X=I;2:M=W,X=Br)were structurall...Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state produced four mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which (1:M=Mo,X=I;2:M=W,X=Br)were structurally determined.Crystals of 1 and 2 are triclinic, space group P(1:a=11.895(3),b=13.107(1),c=20.473(2),α=74.95(6),β=84.87(8),γ=64.27(7)°, Z=2,V=2776.1 ,Rw=0.064 for 6443 observed reflections.2:α=11.876 (1),b=13.065 (2),c= 20.325(2),α=74.95(1),β=85.39(1),γ=64.09(1)°,Z=2,V=2737.3,R_w=0.055 for 5303 observed reflections).The results of the structure determination showed that the central units of the two cubane- like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alter- nate comers.The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.展开更多
The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2] with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)- (S_2CNC_4H_8)_3(O)_2]·0.5CH_...The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2] with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)- (S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P(?),α=12.360(3),b=16.653(6), c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A^3,Z=2,Dc=1.85 g/cm^3, F(000)=962,μ(Mo K_α)=16.53 cm^(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compound may be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2- (μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3 non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi- dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.展开更多
文摘The chemical shifts of 1H-NMR of five Fe_3S_3 cluster compounds were assigned. The main chemical shift values are: δ_ CH_3=1.095-1.946, δ_ CH_2=2.882-3\^803, δ_ C_6H_n=7.547-7.172. In comparison with those of pure (CH_3CH_2)_3N and thiophenol, these values are moved to high position, and the width of these peaks is obviously increased. These characteristics conformed to NMR spectra of paramagnetic compounds and their molecular structures. The paramagnetic property of these compounds was also studied with ESR spectrum. Mass spectra of three compounds were determined. The main fragments were observed, for example, m/z: 130〔(C_2H_5)_4N〕+, 264〔Fe_3S_3〕+, 144〔Fe-S-Fe〕+, 120〔S-Fe-S〕+, 88〔Fe-S〕+, 136〔FeBr〕+, 91〔FeCl〕+ etc. These supported structural characteristics of the anion skeleton and molecules strongly. The possible mechanism of fragmentation was discussed.
文摘The [Zr6(μ2-Cl)12Cl6H4]3- ion with C4v Symmetry in the title compounds has been calculated by DV-Xα program. The calculated results show that ther is almost no available covalence bonding between zirconium atoms and significant Zr 4d AO compositions in the MOs. but there are much stronger Zr-Cl(bridging) bonding. All analysis results suggest that these compounds would be the cluster with Zr6Cl12 cage linked by Zr-Cl bridging bonding plus six Cl teminal ligands rather than the hexazirconium cluster in view of the chemical bonding.
基金financially supported by the Foundation of Fujian Educational Committee(JA14348)
文摘A novel Dy^（3＋） coordination compound,（H_2pipz）（H_3O）[Dy（pydc）_3]·11H_2O（1,pipz = piperazine and H_2pydc = pyridine-2,6-dicarboxylic acid）,has been hydrothermally synthesized and characterized by X-ray single-crystal diffraction,elemental analysis. It is interesting that the packing structure of compound 1 contains 22-core water clusters. Compound 1 is extended into a threedimensional supramolecular structure via O···H···O hydrogen bonding interactions. Furthermore,the luminescent property of compound 1 was also investigated.
文摘By use of self-consistent field Xα scattered-wave (SCF-Xα-SW) method, the electronic structure was calculated for four models of Ti4Al14X (X=Al, Fe, Ni and Cu) clusters. The Ti4Al14X cluster was developed based on L12 Al3Ti-base intermetallic compound. The results are presented using the density of states (DOS) and one-electron properties, such as relative binding tendency between the atom and the model cluster, and hybrid bonding tendency between the alloying element and the host atoms. By comparing the four models of Ti4Al14X cluster, the effect of the Fe, Ni or Cu atom on the physical properties of Al3Ti-based L12 intermetallic compounds is analyzed. The results indicate that the addition of the Fe, Ni or Cu atom intensifies the relative binding tendency between Ti atom and Ti4Al14X cluster. It was found that the Fermi level (EF) lies in a maximum in the DOS for Ti4Al14Al cluster; on the contrary, the EF comes near a minimum tn the DOS for Ti4Al14X (X=Fe, Ni and Cu) cluster. Thus the L12 crystal structure for binary Al3Ti alloy is unstable, and the addition of the Fe, Ni or Cu atom to Al3Ti is benefical to stabilize L12 crystal structure. The calculation also shows that the Fe, Ni or Cu atom strengthens the hybrid bonding tendency between the central atom and the host atoms for Ti4Al14X cluster and thereby may lead to the constriction of the lattice of Al3Ti-base intermetallic compounds.
基金Project supported by the National Natural Science Foundation of China and the State Education Commission of China
文摘Reactions of [NH_4]_2[MS_4](M=Mo,W),CuX(X=Br,I)and PPh_3 in the solid state produced four mixed-metal sulfur containing clusters{Cu_3MS_3X}(PPh_3)_3S(M=Mo,W;X=Br,I),two of which (1:M=Mo,X=I;2:M=W,X=Br)were structurally determined.Crystals of 1 and 2 are triclinic, space group P(1:a=11.895(3),b=13.107(1),c=20.473(2),α=74.95(6),β=84.87(8),γ=64.27(7)°, Z=2,V=2776.1 ,Rw=0.064 for 6443 observed reflections.2:α=11.876 (1),b=13.065 (2),c= 20.325(2),α=74.95(1),β=85.39(1),γ=64.09(1)°,Z=2,V=2737.3,R_w=0.055 for 5303 observed reflections).The results of the structure determination showed that the central units of the two cubane- like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alter- nate comers.The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.
基金Work supported by the National Natural Science Foundation of China.
文摘The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2] with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)- (S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P(?),α=12.360(3),b=16.653(6), c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A^3,Z=2,Dc=1.85 g/cm^3, F(000)=962,μ(Mo K_α)=16.53 cm^(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compound may be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2- (μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3 non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi- dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.
