How to rationally design effective and practical CO_2 adsorbent is a great challenge. Herein, an ultra-microporous metal-organic framework(FJI-H19) with high concentration of free carboxyl groups and uncoordinated Lew...How to rationally design effective and practical CO_2 adsorbent is a great challenge. Herein, an ultra-microporous metal-organic framework(FJI-H19) with high concentration of free carboxyl groups and uncoordinated Lewis basic sites has been synthesized from a multi-dental ligand with a high proportion of polar CO_2-philic atoms. FJI-H19 displays a relatively high CO_2 volumetric uptake(120 cm^3?cm^(–3)) with high selectivity under practical atmosphere(298 K and 1 bar). Further researches demonstrate that such high adsorption results from an unusual synergistic effect from free carboxyl group and uncoordinated N atoms. This result will provide a potential strategy for developing more effective and pratical CO_2 adsorbent based on MOFs.展开更多
The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, ...The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?展开更多
Two new isomeric Au complexes, Au（PPh3）（bmt）, have been synthesized via the reaction of Au（PPh3）CI with 2-benzimidazolethiol （Hbmt） in dichloromethane （CH2Cl2） solution. Their crystal structures were determi...Two new isomeric Au complexes, Au（PPh3）（bmt）, have been synthesized via the reaction of Au（PPh3）CI with 2-benzimidazolethiol （Hbmt） in dichloromethane （CH2Cl2） solution. Their crystal structures were determined by elemental analysis and single-crystal X-ray diffraction studies. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 19.589（2）, b = 21.1368（15）, c = 23.424（2） A, β = 108.346（4）°, V= 9206.1（14） A3, Mr = 1216.85, Dc = 1.756 g/cm3, μ = 6.566 mm^-1, F（000） = 4704, Z = 8, the final R = 0.0563 and wR = 0.1028 for 8125 reflections with I 〉 2σ（I）. Complex 2 crystallizes in the monoclinic system, space group P21/n with a = 9.627（3）, b = 21.384（8）, c = 22.308（8） A, β = 92.068（6）°, V= 4590（3） A3, Mr = 1216.85, Dc = 1.761 g/cms, μ = 6.585 mm^-1, F（000） = 2352, Z = 4, the final R = 0.0500 and wR = 0.0883 for 10477 reflections with I 〉 2σ（i）. X-ray diffraction studies reveal that complexes 1 and 2 both feature a 1D chain along the a axis.展开更多
Metal-organic frameworks(MOFs), consisting of metal, anion and organic ligands, have attracted much attention. The structure of MOFs is affected by various factors. To explore the effects of metal ions, we synthesized...Metal-organic frameworks(MOFs), consisting of metal, anion and organic ligands, have attracted much attention. The structure of MOFs is affected by various factors. To explore the effects of metal ions, we synthesized six complexes, namely {[Me2NH2][Zn4(H2L)(L)]·2 H2O·2 DMF}n(1), {[Me2NH2]2[Cd2(L)]·2H2O}n(2), {[Me2NH2]2[Ca3(L)(μ-OH)2(DMF)2]·2H2O}n(3) and {[Me2NH2]2[M2(L)(μ-OH)]· H2O·2DMF}n(M = Co, 4;Ni, 5;Mn, 6), from a C2v-based hexacarboxylate ligand([1,1’;4’,1’’]terphenyl-3,5,2’,5’,3’’,5’’-hexacarboxylic acid(H6L)) using metal-induced strategy. These MOFs were thoroughly characterized by single-crystal and X-ray diffraction, elemental analysis, Fourier-transform infrared spectra(FTIR) and photoluminescence.展开更多
A new inorganic-organic hybrid supramolecular compound [Habo]6[V10O28]·2C3H7OH·2H2O 1 （abo = R（-）-2-amino-1-butanol） has been synthesized from VO2^＋ in organic solvents and its crystal structure was rep...A new inorganic-organic hybrid supramolecular compound [Habo]6[V10O28]·2C3H7OH·2H2O 1 （abo = R（-）-2-amino-1-butanol） has been synthesized from VO2^＋ in organic solvents and its crystal structure was reported as follows： monoclinic, space group P21/n, a = 11.419（9）, b = 16.811（16）, c = 15.521（12） A, β= 102.98（2）°, V= 2903（4） A^3, Z = 4, C15H46N3O19V5, Mr = 827.25, Dc = 1.893 g/cm^3, 2（MoKα） = 0.71073 A, μ = 1.636 mm^-1, F（000） = 1696, the final R = 0.0696 and wR = 0.1361 for 4641 observed reflections with I 〉 2σ（I）. The compound is based on decavanadate clusters [V10O28]^6-. The hydrogen bonding interactions among Habo^＋ cations, solvents and decavanadate clusters extend 1 into a three-dimensional supramolecular architecture.展开更多
This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<...This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.展开更多
The reactions of nickel group M2+ with thiolate and phosphine inMeOH yield mononuclear and binuclear complexes. Ni2 (PEt3 ), (pdt )2 (pdt = 1, 2propanedithiolate) was synthesized and analyzed by single crystal X--ray ...The reactions of nickel group M2+ with thiolate and phosphine inMeOH yield mononuclear and binuclear complexes. Ni2 (PEt3 ), (pdt )2 (pdt = 1, 2propanedithiolate) was synthesized and analyzed by single crystal X--ray diffractionmethod. The complex is monoclinic with space group P21 /c, Mr= 566. 16 a = 18. 737(5), b=9. 906(4), c= 14. 540(10) A; V=2697. 65 A3, Dc = 1. 394 g/cm3 for Z=4; the final R(Rw) = 0. 062(0. 072). The complex is a dimer, where the Ni atoms arelinked by two sulphur atoms from SC3H6S2- (pdt2- ) ligands and each Ni atom is fourcoordinated by one P and three S atoms with distorted square--planar geometry. The Ni--Ni distance is 3. 025 .A, the average Ni--S, Ni--P distances are 2. 187 and 2. 194A, respectively.展开更多
A novel metal-organic framework[Co(BTTA)(H_(2)O)_(2)]_(n)(FJI-H_(2)4)has been prepared from H_(2)BTTA ligand and CoCl_(2),and its structure was determined by single-crystal X-ray diffraction,thermogravimetric analysis...A novel metal-organic framework[Co(BTTA)(H_(2)O)_(2)]_(n)(FJI-H_(2)4)has been prepared from H_(2)BTTA ligand and CoCl_(2),and its structure was determined by single-crystal X-ray diffraction,thermogravimetric analysis,and Fourier transform infrared spectroscopy.It has relatively narrow pores and high density of open metal ions and free Lewis base sites.Gas adsorption tests demonstrate that FJI-H_(2)4 has moderate CO_(2)(34.0 cm^(3)·g^(–1))and C_(2)H_(2)(53.0 cm^(3)·g^(–1))adsorption capacity,but displays high selectivity of CO_(2)/N_(2)(87)and C_(2)H_(2)/CH_(4)(66)under ambient conditions(298 K,1 atm),which may be attributed to its relatively narrow pores and polar environment.This work will provide a potential strategy for preparing practical porous metal-organic frameworks for gas adsorption and purification.展开更多
Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide(Ln3+)-doped luminescent nanocrystals(NCs) with color-tunable em...Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide(Ln3+)-doped luminescent nanocrystals(NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall(< 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ~10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation(e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence(UCL) ranging from ultraviolet(UV) to visible and to near-infrared(NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.展开更多
Co_6(μ_3-S)_8(Ph_2PCH_2P(O)Ph_2)_6, MW=3012.5, space group R, has the hexagonal parameters, a=26.764(10), c=16.979 (10), V=10532.8~3, Z=3. Mo Kα radiation, λ= 0.71069, Dc=1.425 g/cm^3, μ=9.94 cm^(-3), F(000)=4650,...Co_6(μ_3-S)_8(Ph_2PCH_2P(O)Ph_2)_6, MW=3012.5, space group R, has the hexagonal parameters, a=26.764(10), c=16.979 (10), V=10532.8~3, Z=3. Mo Kα radiation, λ= 0.71069, Dc=1.425 g/cm^3, μ=9.94 cm^(-3), F(000)=4650, R=0.073 and Rw=0.077 for 1965 observed unique reflections with I>3σ(I). The molecular structure consists of a distorted octahed- ral Co_6-core. The Co-Co and Co-S distances fall in the range of 2.805-2.838 and 2.213-2.253, respectively.展开更多
基金supported by the National Natural Science Foundation of China(21390392,21471148)the Youth Innovation Promotion Association CAS
文摘How to rationally design effective and practical CO_2 adsorbent is a great challenge. Herein, an ultra-microporous metal-organic framework(FJI-H19) with high concentration of free carboxyl groups and uncoordinated Lewis basic sites has been synthesized from a multi-dental ligand with a high proportion of polar CO_2-philic atoms. FJI-H19 displays a relatively high CO_2 volumetric uptake(120 cm^3?cm^(–3)) with high selectivity under practical atmosphere(298 K and 1 bar). Further researches demonstrate that such high adsorption results from an unusual synergistic effect from free carboxyl group and uncoordinated N atoms. This result will provide a potential strategy for developing more effective and pratical CO_2 adsorbent based on MOFs.
文摘The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?
基金supported by the Youth Science Foundation of Jining University(2009QNKJ07)
文摘Two new isomeric Au complexes, Au（PPh3）（bmt）, have been synthesized via the reaction of Au（PPh3）CI with 2-benzimidazolethiol （Hbmt） in dichloromethane （CH2Cl2） solution. Their crystal structures were determined by elemental analysis and single-crystal X-ray diffraction studies. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 19.589（2）, b = 21.1368（15）, c = 23.424（2） A, β = 108.346（4）°, V= 9206.1（14） A3, Mr = 1216.85, Dc = 1.756 g/cm3, μ = 6.566 mm^-1, F（000） = 4704, Z = 8, the final R = 0.0563 and wR = 0.1028 for 8125 reflections with I 〉 2σ（I）. Complex 2 crystallizes in the monoclinic system, space group P21/n with a = 9.627（3）, b = 21.384（8）, c = 22.308（8） A, β = 92.068（6）°, V= 4590（3） A3, Mr = 1216.85, Dc = 1.761 g/cms, μ = 6.585 mm^-1, F（000） = 2352, Z = 4, the final R = 0.0500 and wR = 0.0883 for 10477 reflections with I 〉 2σ（i）. X-ray diffraction studies reveal that complexes 1 and 2 both feature a 1D chain along the a axis.
基金Financially supported by the Natural Science Foundation of Shandong Province(ZR2017BB023)China Postdoctoral Science Foundation(2016M602180)Innovative Training Project for graduate Students of Shandong Normal University
文摘Metal-organic frameworks(MOFs), consisting of metal, anion and organic ligands, have attracted much attention. The structure of MOFs is affected by various factors. To explore the effects of metal ions, we synthesized six complexes, namely {[Me2NH2][Zn4(H2L)(L)]·2 H2O·2 DMF}n(1), {[Me2NH2]2[Cd2(L)]·2H2O}n(2), {[Me2NH2]2[Ca3(L)(μ-OH)2(DMF)2]·2H2O}n(3) and {[Me2NH2]2[M2(L)(μ-OH)]· H2O·2DMF}n(M = Co, 4;Ni, 5;Mn, 6), from a C2v-based hexacarboxylate ligand([1,1’;4’,1’’]terphenyl-3,5,2’,5’,3’’,5’’-hexacarboxylic acid(H6L)) using metal-induced strategy. These MOFs were thoroughly characterized by single-crystal and X-ray diffraction, elemental analysis, Fourier-transform infrared spectra(FTIR) and photoluminescence.
基金This work was supported by the National Natural Science Foundation of China and Natural Science Foundation of Fujian Province
文摘A new inorganic-organic hybrid supramolecular compound [Habo]6[V10O28]·2C3H7OH·2H2O 1 （abo = R（-）-2-amino-1-butanol） has been synthesized from VO2^＋ in organic solvents and its crystal structure was reported as follows： monoclinic, space group P21/n, a = 11.419（9）, b = 16.811（16）, c = 15.521（12） A, β= 102.98（2）°, V= 2903（4） A^3, Z = 4, C15H46N3O19V5, Mr = 827.25, Dc = 1.893 g/cm^3, 2（MoKα） = 0.71073 A, μ = 1.636 mm^-1, F（000） = 1696, the final R = 0.0696 and wR = 0.1361 for 4641 observed reflections with I 〉 2σ（I）. The compound is based on decavanadate clusters [V10O28]^6-. The hydrogen bonding interactions among Habo^＋ cations, solvents and decavanadate clusters extend 1 into a three-dimensional supramolecular architecture.
文摘This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.
文摘The reactions of nickel group M2+ with thiolate and phosphine inMeOH yield mononuclear and binuclear complexes. Ni2 (PEt3 ), (pdt )2 (pdt = 1, 2propanedithiolate) was synthesized and analyzed by single crystal X--ray diffractionmethod. The complex is monoclinic with space group P21 /c, Mr= 566. 16 a = 18. 737(5), b=9. 906(4), c= 14. 540(10) A; V=2697. 65 A3, Dc = 1. 394 g/cm3 for Z=4; the final R(Rw) = 0. 062(0. 072). The complex is a dimer, where the Ni atoms arelinked by two sulphur atoms from SC3H6S2- (pdt2- ) ligands and each Ni atom is fourcoordinated by one P and three S atoms with distorted square--planar geometry. The Ni--Ni distance is 3. 025 .A, the average Ni--S, Ni--P distances are 2. 187 and 2. 194A, respectively.
基金supported by the National Natural Science Foundation of China (21871265)the Youth Innovation Promotion Association CAS
文摘A novel metal-organic framework[Co(BTTA)(H_(2)O)_(2)]_(n)(FJI-H_(2)4)has been prepared from H_(2)BTTA ligand and CoCl_(2),and its structure was determined by single-crystal X-ray diffraction,thermogravimetric analysis,and Fourier transform infrared spectroscopy.It has relatively narrow pores and high density of open metal ions and free Lewis base sites.Gas adsorption tests demonstrate that FJI-H_(2)4 has moderate CO_(2)(34.0 cm^(3)·g^(–1))and C_(2)H_(2)(53.0 cm^(3)·g^(–1))adsorption capacity,but displays high selectivity of CO_(2)/N_(2)(87)and C_(2)H_(2)/CH_(4)(66)under ambient conditions(298 K,1 atm),which may be attributed to its relatively narrow pores and polar environment.This work will provide a potential strategy for preparing practical porous metal-organic frameworks for gas adsorption and purification.
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences (CASXDB20000000)+3 种基金the National Natural Science Foundation of China (NSFCNos. 21871256 and 21731006)the Key Research Program of Frontier Science CAS (QYZDY-SSW-SLH025)the Outstanding Youth Innovation Promotion Association of CAS。
文摘Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide(Ln3+)-doped luminescent nanocrystals(NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall(< 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ~10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation(e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence(UCL) ranging from ultraviolet(UV) to visible and to near-infrared(NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.
基金Project supported by the National Natural Science Foundation of China.
文摘Co_6(μ_3-S)_8(Ph_2PCH_2P(O)Ph_2)_6, MW=3012.5, space group R, has the hexagonal parameters, a=26.764(10), c=16.979 (10), V=10532.8~3, Z=3. Mo Kα radiation, λ= 0.71069, Dc=1.425 g/cm^3, μ=9.94 cm^(-3), F(000)=4650, R=0.073 and Rw=0.077 for 1965 observed unique reflections with I>3σ(I). The molecular structure consists of a distorted octahed- ral Co_6-core. The Co-Co and Co-S distances fall in the range of 2.805-2.838 and 2.213-2.253, respectively.
