The specific heat capacities of Cu60Zr20Hfl0Til0 bulk metallic glass （BMG） and crystallized alloys were measured from 2 to 101 K. The effect of crystallization on the specific heat capacity of the BMG was studied. T...The specific heat capacities of Cu60Zr20Hfl0Til0 bulk metallic glass （BMG） and crystallized alloys were measured from 2 to 101 K. The effect of crystallization on the specific heat capacity of the BMG was studied. The effects of crystallization and the relationship between local modes and boson peak in the BMG were discussed. The specific heat capacity deviates from the simple Debye behaviors, showing the presence of local harmonic modes （Einstein oscillator） in the BMG and the crystallized alloy. Model calculation includes the contribution of one Debye mode and two Einstein modes for the BMG, one Debye mode and one Einstein mode for the crystallized alloy, showing an adequate description of the experimental data.展开更多
A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was charac...A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.0293（3）, b = 2.0293（3）, c = 1.3758（2） nm, α =β= γ = 90°, V= 5.6657（13） nm3, Dc= 1.379 g/cm3, Z = 8, μ（MoKa） = 0.815 mm-1, Mr = 588.14, F（000） = 2456, S = 1.047, R = 0.0459 and wR = 0.1053. The crystal structure shows that two neighboring Cu（Ⅱ） ions are linked together by one bridging-chelating 2,4,6-trimethyl-benzoic group, forming a one-dimensional chain structure. Each Cu（Ⅱ） ion is coordinated with two nitrogen atoms from one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethyl-benzoic acid molecules and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. The cyclic voltammetry behavior of the complex was also investigated.展开更多
A new cooper benzenedicarboxylate metal-organic coordination polymer,[Cu（μH2O）（BDC）]n·nDMF（1,H2BDC = 1,4-benzenedicarboxylate acid,DMF = N,N＇-dimethylfor-mamide）,has been successfully synthesized under hy...A new cooper benzenedicarboxylate metal-organic coordination polymer,[Cu（μH2O）（BDC）]n·nDMF（1,H2BDC = 1,4-benzenedicarboxylate acid,DMF = N,N＇-dimethylfor-mamide）,has been successfully synthesized under hydrothermal conditions and characterized by IR spectroscopy,elemental analysis,thermogravimetric analysis and single-crystal X-ray diffraction.This complex crystallizes in triclinic,space group P1 with a = 6.605,b = 10.44780（10）,c = 11.0881（6） ,α = 62.064（11）,β = 73.410（15）,γ = 78.404（16）°,C11H13CuNO6,Mr = 318.76,V = 645.79（8） 3,Z = 2,Dc = 1.639 g/cm3,F（000） = 326,μ = 1.712 mm-1,the final R = 0.0362 and wR = 0.1330 for 2055 observed reflections with I 〉 2σ（I）.The title compound contains infinite inorganic chains constructed by Cu oxygen octahedra by sharing corners and edges.Each chain is connected by BDC linkers to four other chains to form a three-dimensional framework with irregular rhombic channels where the DMF molecules are encapsulated.展开更多
The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was d...The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831（12）, b = 11.6718（13）, c = 11.7771（13）, α = 105.392（2）, β = 108.382（2）, γ = 112.397（2）o, CuC28H20N2O8, Mr = 576.00, V = 1222.4（2）3, Dc = 1.565 g/cm3, F（000） = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I 2σ（I）. The title complex has a 1D [Cu（bbpy）（H2bptc）]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C–H···π interactions to form a 3D metal-organic framework.展开更多
A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analys...A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex： monoclinic, space group C2/c, a = 19.214（3）, b = 10.6973（14）, c = 22.567（3） A, β = 105.081（2）°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F（000） = 2160, V= 4478.6（10） A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 （Rint = 1.0357） independent reflections and 3290 observed ones （I 〉 2σ（I））. Structural analysis shows that coordination geometry of Cu（ Ⅱ ） is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.展开更多
Crystallization growth of single-crystal Cu by continuous casting has been investigated using self-designed horizontal continuous casting equipment and XRD. Experimental results showed that the crystallization plane o...Crystallization growth of single-crystal Cu by continuous casting has been investigated using self-designed horizontal continuous casting equipment and XRD. Experimental results showed that the crystallization plane of (311), (220) and (ill) were eliminated sequentially in evolutionary process. The final growth plane of crystal was (200), the direction of crystallization was [100], the growth direction of both sides of the rod inclined to axis, and the degree of deviation of direction [100] from the crystal axis was less than 10°. In order to produce high quality single crystal, the solid-liquid interface morphology must be smooth, even be planar.展开更多
A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a =...A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.展开更多
Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and...Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.展开更多
A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP a...A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.展开更多
基金Project(082102230035)supported by the Foundation of Science and Technology Department of Henan Province,China
文摘The specific heat capacities of Cu60Zr20Hfl0Til0 bulk metallic glass （BMG） and crystallized alloys were measured from 2 to 101 K. The effect of crystallization on the specific heat capacity of the BMG was studied. The effects of crystallization and the relationship between local modes and boson peak in the BMG were discussed. The specific heat capacity deviates from the simple Debye behaviors, showing the presence of local harmonic modes （Einstein oscillator） in the BMG and the crystallized alloy. Model calculation includes the contribution of one Debye mode and two Einstein modes for the BMG, one Debye mode and one Einstein mode for the crystallized alloy, showing an adequate description of the experimental data.
基金supported by the Key Laboratory of Micro-systems and Micro-structures Manufacturing of Ministry of Education,Harbin Institute of Technology,China(No.2020KM005)the Natural Science Foundation of Heilongjiang Province,China(No.YQ2020E030)。
基金supported by the Foundation of Education Committee of Hunan Province(06C195)the Research Award Fund for Outstanding Young Teachers of Hengyang Normal University(2006)Supported by the construct program of the key discipline in hunan province.
文摘A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.0293（3）, b = 2.0293（3）, c = 1.3758（2） nm, α =β= γ = 90°, V= 5.6657（13） nm3, Dc= 1.379 g/cm3, Z = 8, μ（MoKa） = 0.815 mm-1, Mr = 588.14, F（000） = 2456, S = 1.047, R = 0.0459 and wR = 0.1053. The crystal structure shows that two neighboring Cu（Ⅱ） ions are linked together by one bridging-chelating 2,4,6-trimethyl-benzoic group, forming a one-dimensional chain structure. Each Cu（Ⅱ） ion is coordinated with two nitrogen atoms from one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethyl-benzoic acid molecules and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. The cyclic voltammetry behavior of the complex was also investigated.
基金supported by 973 Program (2011CB932504)NNSFC (20971121)NSF of Fujian Province
文摘A new cooper benzenedicarboxylate metal-organic coordination polymer,[Cu（μH2O）（BDC）]n·nDMF（1,H2BDC = 1,4-benzenedicarboxylate acid,DMF = N,N＇-dimethylfor-mamide）,has been successfully synthesized under hydrothermal conditions and characterized by IR spectroscopy,elemental analysis,thermogravimetric analysis and single-crystal X-ray diffraction.This complex crystallizes in triclinic,space group P1 with a = 6.605,b = 10.44780（10）,c = 11.0881（6） ,α = 62.064（11）,β = 73.410（15）,γ = 78.404（16）°,C11H13CuNO6,Mr = 318.76,V = 645.79（8） 3,Z = 2,Dc = 1.639 g/cm3,F（000） = 326,μ = 1.712 mm-1,the final R = 0.0362 and wR = 0.1330 for 2055 observed reflections with I 〉 2σ（I）.The title compound contains infinite inorganic chains constructed by Cu oxygen octahedra by sharing corners and edges.Each chain is connected by BDC linkers to four other chains to form a three-dimensional framework with irregular rhombic channels where the DMF molecules are encapsulated.
基金Supported by the National Natural Science Foundation of China (No. 10947162)the Natural Science Foundation of Henan Province (No. 2010A140009)the International Technology Cooperation Project of Science and Technology Department of Henan Province (No. 104300510044)
文摘The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831（12）, b = 11.6718（13）, c = 11.7771（13）, α = 105.392（2）, β = 108.382（2）, γ = 112.397（2）o, CuC28H20N2O8, Mr = 576.00, V = 1222.4（2）3, Dc = 1.565 g/cm3, F（000） = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I 2σ（I）. The title complex has a 1D [Cu（bbpy）（H2bptc）]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C–H···π interactions to form a 3D metal-organic framework.
基金Project supported by the National Natural Science Foundation of China (No. 20671064)Foundation of Education Committee of Liaoning Province (No. 2005336)
文摘A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex： monoclinic, space group C2/c, a = 19.214（3）, b = 10.6973（14）, c = 22.567（3） A, β = 105.081（2）°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F（000） = 2160, V= 4478.6（10） A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 （Rint = 1.0357） independent reflections and 3290 observed ones （I 〉 2σ（I））. Structural analysis shows that coordination geometry of Cu（ Ⅱ ） is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.
文摘Crystallization growth of single-crystal Cu by continuous casting has been investigated using self-designed horizontal continuous casting equipment and XRD. Experimental results showed that the crystallization plane of (311), (220) and (ill) were eliminated sequentially in evolutionary process. The final growth plane of crystal was (200), the direction of crystallization was [100], the growth direction of both sides of the rod inclined to axis, and the degree of deviation of direction [100] from the crystal axis was less than 10°. In order to produce high quality single crystal, the solid-liquid interface morphology must be smooth, even be planar.
文摘A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.
基金financially supported by the National Natural Science Foundation of China(21302003)the Science and Technology Project of Henan Province(No.182102210200)
文摘Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.
基金supported by the National Natural Science Foundation of China(51172232)
文摘A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.
