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2014 Volume 33 Issue 8
2014, 33(8): 1109-1116
Abstract:
Nine phthalates were calculated at the B3LYP/6-311G** level using DFT method. The corresponding linear relationship equations (R2 were 0.853 and 0.936 respectively) for the biodegradation rate (Kb) and half-life time (t1/2) of biodegradation were obtained with the structural parameters as theoretical descriptors. Furthermore, CoMFA method was also applied to establish 3D models which revealed the fields influencing these properties. The relationship between the properties and the structure was obtained. The correlation coefficients of the models were 0.992 and 0.999, respectively. Analyses of 2D and 3D models demonstrated that the molecular volume was an important factor affecting the biodegradability of these compounds.
Nine phthalates were calculated at the B3LYP/6-311G** level using DFT method. The corresponding linear relationship equations (R2 were 0.853 and 0.936 respectively) for the biodegradation rate (Kb) and half-life time (t1/2) of biodegradation were obtained with the structural parameters as theoretical descriptors. Furthermore, CoMFA method was also applied to establish 3D models which revealed the fields influencing these properties. The relationship between the properties and the structure was obtained. The correlation coefficients of the models were 0.992 and 0.999, respectively. Analyses of 2D and 3D models demonstrated that the molecular volume was an important factor affecting the biodegradability of these compounds.
2014, 33(8): 1117-1122
Abstract:
The title compound (C50H44O10) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a=16.713(4), b=13.189(3), c=19.434(5) Å, β=104.411(4)°, Mr=804.85, Dc=1.288 g/cm3, V=4149.2(17) Å3, Z=4, F(000)=1696, μ(MoKa)=0.089 mm-1, T=296(2) K, 7279 independent reflections with 3172 observed ones (I>2σ(I)), R=0.0520 and wR=0.1203 with GOF=0.928 (R=0.1464 and wR=0.1657 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O-H…O hydrogen bonds. Preliminary bioassays indicated that the title compound has a potent inhibitory activity against the strand transfer process of HIV-1 integrase.
The title compound (C50H44O10) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a=16.713(4), b=13.189(3), c=19.434(5) Å, β=104.411(4)°, Mr=804.85, Dc=1.288 g/cm3, V=4149.2(17) Å3, Z=4, F(000)=1696, μ(MoKa)=0.089 mm-1, T=296(2) K, 7279 independent reflections with 3172 observed ones (I>2σ(I)), R=0.0520 and wR=0.1203 with GOF=0.928 (R=0.1464 and wR=0.1657 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O-H…O hydrogen bonds. Preliminary bioassays indicated that the title compound has a potent inhibitory activity against the strand transfer process of HIV-1 integrase.
2014, 33(8): 1123-1128
Abstract:
The title compound Δ14,15-anhydro-24-thiocarbonylbufalin (1) was prepared by the reaction of natural product bufalin with Lawesson reagent. The crystal structure of 1, C24H30O2S·C24H30O2S, was determined by single-crystal X-ray diffraction analysis. It belongs to monoclinic, space group C2, with a=30.9845(2), b=6.8036(3), c=22.5791(15) Å, V=4241.7(4) Å3, Mr=384.21, Z=4, Dc=1.204 g/cm3, μ=1.463 mm-1, F(000)=1664, S=1.064, R=0.0487 and wR=0.0645 for 4683 unique reflections, of which 3757 were observed (I>2σ(I)). The asymmetric unit contains two independent molecules (I and Ⅱ), which are closely similar to each other except for the orientation of the lactone ring. Both conformations of I and Ⅱ are in good agreement with the solution structure in methanol as indicated by 1H-NMR analysis. Due to the presence of heavy atom sulfur in the molecules, the final refinement resulted in a small Flack parameter 0.02(3), permitting the assignments of the absolute configuration. In the solid state, intermolecular hydrogen bonds involving thiocarbonyl group in the lactone moiety and the hydroxyl groups in the steroid moiety ester linked adjacent molecules into a three-dimensional network. Compound 1 showed weak inhibition on Na+/K+-ATPase in contrast to the strong inhibitory activity of the parent compound bufalin, suggesting that the carbonyl group in lactone moiety and the hydroxyl group at C-14 play important roles for the inhibition of Na+/K+-ATPase.
The title compound Δ14,15-anhydro-24-thiocarbonylbufalin (1) was prepared by the reaction of natural product bufalin with Lawesson reagent. The crystal structure of 1, C24H30O2S·C24H30O2S, was determined by single-crystal X-ray diffraction analysis. It belongs to monoclinic, space group C2, with a=30.9845(2), b=6.8036(3), c=22.5791(15) Å, V=4241.7(4) Å3, Mr=384.21, Z=4, Dc=1.204 g/cm3, μ=1.463 mm-1, F(000)=1664, S=1.064, R=0.0487 and wR=0.0645 for 4683 unique reflections, of which 3757 were observed (I>2σ(I)). The asymmetric unit contains two independent molecules (I and Ⅱ), which are closely similar to each other except for the orientation of the lactone ring. Both conformations of I and Ⅱ are in good agreement with the solution structure in methanol as indicated by 1H-NMR analysis. Due to the presence of heavy atom sulfur in the molecules, the final refinement resulted in a small Flack parameter 0.02(3), permitting the assignments of the absolute configuration. In the solid state, intermolecular hydrogen bonds involving thiocarbonyl group in the lactone moiety and the hydroxyl groups in the steroid moiety ester linked adjacent molecules into a three-dimensional network. Compound 1 showed weak inhibition on Na+/K+-ATPase in contrast to the strong inhibitory activity of the parent compound bufalin, suggesting that the carbonyl group in lactone moiety and the hydroxyl group at C-14 play important roles for the inhibition of Na+/K+-ATPase.
2014, 33(8): 1129-1134
Abstract:
The novel title compound 1-(4-methoxybenzylidene)-2-(1-phenyl-6-trifluoromethyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)hydrazine monohydrate (C20H15F3N6O·H2O, Mr=430.40) has been synthesized by a four-step procedure including the cyclization, chlorination, hydrazinolysis and condensation reaction, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbca with a=8.3779(13), b=17.607(3), c=26.774(4) Å, V=3949.2(11) Å3, Z=8, Dc=1.448 g/cm3, μ=0.117 mm-1, F(000)=1776, the final R=0.0553 and wR=0.1516 for 2354 observed reflections with I>2σ(I). X-ray diffraction analysis reveals that the title compound is almost coplanar except for the trifluoromethyl and phenyl moieties. In the crystal packing, the molecules are linked by intermolecular O(1W)-H(1WA)…N(2), O(1W)-H(1WA)…N(4) and N(5)-H(5A)…O(1W) hydrogen bonds via water molecules and stacked through π-π stacking interactions. The preliminary bioassay suggested that the title compound exhibits relatively good antitumor activity against HepG2 and BCG-823.
The novel title compound 1-(4-methoxybenzylidene)-2-(1-phenyl-6-trifluoromethyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)hydrazine monohydrate (C20H15F3N6O·H2O, Mr=430.40) has been synthesized by a four-step procedure including the cyclization, chlorination, hydrazinolysis and condensation reaction, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbca with a=8.3779(13), b=17.607(3), c=26.774(4) Å, V=3949.2(11) Å3, Z=8, Dc=1.448 g/cm3, μ=0.117 mm-1, F(000)=1776, the final R=0.0553 and wR=0.1516 for 2354 observed reflections with I>2σ(I). X-ray diffraction analysis reveals that the title compound is almost coplanar except for the trifluoromethyl and phenyl moieties. In the crystal packing, the molecules are linked by intermolecular O(1W)-H(1WA)…N(2), O(1W)-H(1WA)…N(4) and N(5)-H(5A)…O(1W) hydrogen bonds via water molecules and stacked through π-π stacking interactions. The preliminary bioassay suggested that the title compound exhibits relatively good antitumor activity against HepG2 and BCG-823.
2014, 33(8): 1135-1140
Abstract:
A new tetranuclear cluster [Co4(bm)6Cl2]·(H2O)2·(CH3OH) (1, Hbm is (1H-benzimidazol-2-yl)-methanol) has been synthesized by solvothermal method and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. Complex 1 belongs to monoclinic space group P21/n with a=21.1713(5), b=12.7948(3), c=24.0195(9) Å, β=95.309(3)°, V=6478.6(3) Å3, Z=4, F(000)=2568, Dc=1.289 g·cm-3, Mr=1257.63, μ=9.096 mm-1, S=1.000, the final R=0.0861 and wR=0.2552 for 4956 observed reflections with I>2σ(I). Two connected face-sharing cubes are observed in the framework of 1, each with one vertex missing. Complex 1 forms a 2-D network through N-H…O hydrogen bonds. The apparent holes can be observed.
A new tetranuclear cluster [Co4(bm)6Cl2]·(H2O)2·(CH3OH) (1, Hbm is (1H-benzimidazol-2-yl)-methanol) has been synthesized by solvothermal method and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. Complex 1 belongs to monoclinic space group P21/n with a=21.1713(5), b=12.7948(3), c=24.0195(9) Å, β=95.309(3)°, V=6478.6(3) Å3, Z=4, F(000)=2568, Dc=1.289 g·cm-3, Mr=1257.63, μ=9.096 mm-1, S=1.000, the final R=0.0861 and wR=0.2552 for 4956 observed reflections with I>2σ(I). Two connected face-sharing cubes are observed in the framework of 1, each with one vertex missing. Complex 1 forms a 2-D network through N-H…O hydrogen bonds. The apparent holes can be observed.
2014, 33(8): 1141-1146
Abstract:
Two new zinc bipyridinium compounds, [N-ethyl-4,4'-bipyridinium][ZnX4] (X=Cl (1) or Br (2)) with N-ethyl-4,4'-bipyridinium generated in situ, have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Both compounds are isostructural and crystallize in the P21/c space group of monoclinic system. Compound 1: a=8.4397(5), b=21.988(1), c=8.8777(5) Å, β=106.490(1)°, V=1579.7(2) Å3, C12H15Cl4N2Zn, Mr=394.43, Z=4, Dc=1.658 g/cm3, S=1.068, μ(MoKα)=2.218 mm-1, F(000)=796, R=0.0295 and wR=0.0766. Compound 2: a=8.4154(6), b=22.844(2), c=9.0308(7) Å, β=106.026(1)°, V=1668.6(2) Å3, C12H15Br4N2Zn, Mr=572.27, Z=4, Dc=2.278 g/cm3, S=1.033, μ(MoKα)=11.038 mm-1, F(000)=1084, R=0.0427 and wR=0.1175. Both of them are characteristic of an isolated structure with the zinc atoms locating at a tetrahedral environment. In both compounds, the N-ethyl-4,4'-bipyridinium2+ cations and ZnX42- anions interconnect together via hydrogen bonding interactions to construct a three-dimensional (3-D) supramolecular framework. Fluorescent studies reveal that both compounds exhibit a strong emission in the green region. In combination with the theoretical calculations, we can draw a conclusion that the emissions should result from ligand-toligand charge-transfer (LLCT) transition.
Two new zinc bipyridinium compounds, [N-ethyl-4,4'-bipyridinium][ZnX4] (X=Cl (1) or Br (2)) with N-ethyl-4,4'-bipyridinium generated in situ, have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Both compounds are isostructural and crystallize in the P21/c space group of monoclinic system. Compound 1: a=8.4397(5), b=21.988(1), c=8.8777(5) Å, β=106.490(1)°, V=1579.7(2) Å3, C12H15Cl4N2Zn, Mr=394.43, Z=4, Dc=1.658 g/cm3, S=1.068, μ(MoKα)=2.218 mm-1, F(000)=796, R=0.0295 and wR=0.0766. Compound 2: a=8.4154(6), b=22.844(2), c=9.0308(7) Å, β=106.026(1)°, V=1668.6(2) Å3, C12H15Br4N2Zn, Mr=572.27, Z=4, Dc=2.278 g/cm3, S=1.033, μ(MoKα)=11.038 mm-1, F(000)=1084, R=0.0427 and wR=0.1175. Both of them are characteristic of an isolated structure with the zinc atoms locating at a tetrahedral environment. In both compounds, the N-ethyl-4,4'-bipyridinium2+ cations and ZnX42- anions interconnect together via hydrogen bonding interactions to construct a three-dimensional (3-D) supramolecular framework. Fluorescent studies reveal that both compounds exhibit a strong emission in the green region. In combination with the theoretical calculations, we can draw a conclusion that the emissions should result from ligand-toligand charge-transfer (LLCT) transition.
2014, 33(8): 1147-1153
Abstract:
Reactions of NaAcebiim (NaAcebiim=1-acetic acid-2, 2'-biimidazole monosodium salt) and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd(Acebiim)(NO3)(H2O)]n (1) and 0D [Zn(Acebiim)2(H2O)2]·2H2O (2) in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group P1, and 2 is of monoclinic system, space group P21/n. In 1, two nitrate groups link two Cd(Ⅱ) ions forming [Cd2(NO3)2(H2O)2] as secondary building units that are interconnected by the Acebiim-ligand into an infinite ladder. In 2, the hydrogen-bonded synthon R22(16) between the N-H moieties and carboxylic acid link [Zn(Acebiim)2(H2O)2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.
Reactions of NaAcebiim (NaAcebiim=1-acetic acid-2, 2'-biimidazole monosodium salt) and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd(Acebiim)(NO3)(H2O)]n (1) and 0D [Zn(Acebiim)2(H2O)2]·2H2O (2) in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group P1, and 2 is of monoclinic system, space group P21/n. In 1, two nitrate groups link two Cd(Ⅱ) ions forming [Cd2(NO3)2(H2O)2] as secondary building units that are interconnected by the Acebiim-ligand into an infinite ladder. In 2, the hydrogen-bonded synthon R22(16) between the N-H moieties and carboxylic acid link [Zn(Acebiim)2(H2O)2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.
2014, 33(8): 1154-1158
Abstract:
A chiral 3D metal-organic framework [CdL]·DMSO·H2O (1) was constructed by an N-methyl substituted salan ligand (H2L), and characterized by elemental analyses, IR, TGA, powder XRD and single-crystal X-ray crystallography. 1 crystallizes in the chiral hexagonal space group P6522 with a=b=12.2175(3), c=51.450(3) Å, V=6650.9(4) Å3, Z=6, Mr=883.45, Dc=1.323 g·cm-3, F(000)=2760, λ(CuKα)=1.54178 Å, μ=4.771 mm-1, GOOF=1.041, R=0.0313 for 3901 observed reflections with I>2σ(I) and wR=0.0773. 1 consists of three identical sets of independent 3D frameworks interpenetrated with each other. In each set of such 3D frameworks, one half of the monomer (CdL)1/2 as the building unit forms double antiparrel helical chains which are further bridged together by other (CdL)1/2 units from adjacent helical chains. All CdL units in 1 adopt Δ geometry. DMSO and water guest molecules are found in the gap of the interpenetrated frameworks.
A chiral 3D metal-organic framework [CdL]·DMSO·H2O (1) was constructed by an N-methyl substituted salan ligand (H2L), and characterized by elemental analyses, IR, TGA, powder XRD and single-crystal X-ray crystallography. 1 crystallizes in the chiral hexagonal space group P6522 with a=b=12.2175(3), c=51.450(3) Å, V=6650.9(4) Å3, Z=6, Mr=883.45, Dc=1.323 g·cm-3, F(000)=2760, λ(CuKα)=1.54178 Å, μ=4.771 mm-1, GOOF=1.041, R=0.0313 for 3901 observed reflections with I>2σ(I) and wR=0.0773. 1 consists of three identical sets of independent 3D frameworks interpenetrated with each other. In each set of such 3D frameworks, one half of the monomer (CdL)1/2 as the building unit forms double antiparrel helical chains which are further bridged together by other (CdL)1/2 units from adjacent helical chains. All CdL units in 1 adopt Δ geometry. DMSO and water guest molecules are found in the gap of the interpenetrated frameworks.
2014, 33(8): 1159-1163
Abstract:
A new magnetic MOF with cyclic triazolate and linear azido mediators, [Co2(trz)3(N3)]n 1 (trz-=1,2,4-triazolate), was hydrothermally synthesized and structurally and magnetically characterized. 1 crystallizes in the rhombohedral P63/mmc space group with a=b=10.0716(17), c=7.5860(14) Å, V=666.4(2) Å3, Dc=1.814 g/cm3, Mr=364.09, Z=2, F(000)=360, μ=2.499 mm-1, the final R=0.0676 and wR=0.1952 for 229 observed reflections with I>2σ(I). Complex 1 consists of linear {Co(trz)3}n chains passing through a C6 rotation axis, which are interconnected with tetrahedral CoⅡ ion by μ3-trz- ligands into a hexagonal three-dimensional antiferromagnetic framework.
A new magnetic MOF with cyclic triazolate and linear azido mediators, [Co2(trz)3(N3)]n 1 (trz-=1,2,4-triazolate), was hydrothermally synthesized and structurally and magnetically characterized. 1 crystallizes in the rhombohedral P63/mmc space group with a=b=10.0716(17), c=7.5860(14) Å, V=666.4(2) Å3, Dc=1.814 g/cm3, Mr=364.09, Z=2, F(000)=360, μ=2.499 mm-1, the final R=0.0676 and wR=0.1952 for 229 observed reflections with I>2σ(I). Complex 1 consists of linear {Co(trz)3}n chains passing through a C6 rotation axis, which are interconnected with tetrahedral CoⅡ ion by μ3-trz- ligands into a hexagonal three-dimensional antiferromagnetic framework.
2014, 33(8): 1164-1170
Abstract:
Two new low dimensional lead(Ⅱ) diiodide complexes with 1,10-phenanthroline-5,6-dione (Phendione), PbI2(Phendione)2 (1) and PbI2(Phendione)(DMSO)2 (2), have been synthesized by solution processes and structurally determined by X-ray diffraction method. Both compounds are mononuclear with the lead centers being in highly distorted octahedral environments. Hydrogen bonds and π-π stacking interactions contribute to the structural extension and stabilization. Theoretical calculations based on the DFT/B3LYP level indicate that the introduction of electronic donating groups on the phenanthroline ring can improve the electron density of nitrogen atoms, and they can replace part of the bridged iodine atoms to lower the structural dimensions. Experimental band gaps of about 2.07 and 1.97 eV indicate their semiconductor nature.
Two new low dimensional lead(Ⅱ) diiodide complexes with 1,10-phenanthroline-5,6-dione (Phendione), PbI2(Phendione)2 (1) and PbI2(Phendione)(DMSO)2 (2), have been synthesized by solution processes and structurally determined by X-ray diffraction method. Both compounds are mononuclear with the lead centers being in highly distorted octahedral environments. Hydrogen bonds and π-π stacking interactions contribute to the structural extension and stabilization. Theoretical calculations based on the DFT/B3LYP level indicate that the introduction of electronic donating groups on the phenanthroline ring can improve the electron density of nitrogen atoms, and they can replace part of the bridged iodine atoms to lower the structural dimensions. Experimental band gaps of about 2.07 and 1.97 eV indicate their semiconductor nature.
2014, 33(8): 1171-1183
Abstract:
The employment of N-hydroxy-pyridine-2-carboxamidine in the coordination chemistry of zinc(Ⅱ), nickel(Ⅱ) and manganese(Ⅱ) under solvothermal conditions is reported. Four complexes of compositions, [Zn2(O2CMe)3{(py)C(NH2)NOH}4](OH) (1), [Zn4(OH)2{(py)C(NH2)-NO}4Cl2]·MeCN (2), [Ni(SO4)(H2O){(py)C(NH2)NOH}2]·H2O (3) and [Mn(SO4){(py)C(NH2)-NOH}2]n (4), have been synthesized by rationally choosing different metal salts and dexterously employing acetate and sulfate ions as the bridging groups. Luminescent properties for 2 suggested strong emission in the solid state at room temperature. Variable temperature (2.0~300 K) magnetic studies for the linear chain complex 4 indicate weak antiferromagnetic Mn(Ⅱ)…Mn(Ⅱ) exchange interactions.
The employment of N-hydroxy-pyridine-2-carboxamidine in the coordination chemistry of zinc(Ⅱ), nickel(Ⅱ) and manganese(Ⅱ) under solvothermal conditions is reported. Four complexes of compositions, [Zn2(O2CMe)3{(py)C(NH2)NOH}4](OH) (1), [Zn4(OH)2{(py)C(NH2)-NO}4Cl2]·MeCN (2), [Ni(SO4)(H2O){(py)C(NH2)NOH}2]·H2O (3) and [Mn(SO4){(py)C(NH2)-NOH}2]n (4), have been synthesized by rationally choosing different metal salts and dexterously employing acetate and sulfate ions as the bridging groups. Luminescent properties for 2 suggested strong emission in the solid state at room temperature. Variable temperature (2.0~300 K) magnetic studies for the linear chain complex 4 indicate weak antiferromagnetic Mn(Ⅱ)…Mn(Ⅱ) exchange interactions.
2014, 33(8): 1184-1190
Abstract:
[Pb(TPT)(μ-I)2PbI2(μ-I)2Pb(TPT)] 1 (TPT is the abbreviation of 3,5,6-tris(2-pyridyl)-1,2,4-triazine ligand) has been synthesized and characterized by elemental analysis, IR, 1HNMR spectroscopy and studied by thermal and electrochemical properties as well as X-ray crystallography. The single-crystal X-ray data show two different kinds of Pb2+ ions in 1 with coordination numbers of six, Pb1=PbI6, and five, Pb2=PbN3I2, with holodirected and hemidirected coordination spheres, respectively. The supramolecular features in 1 are negotiated through the weak but directional Pb…I, C-H…N and C-H…I interactions and aromatic π-π stacking interactions.
[Pb(TPT)(μ-I)2PbI2(μ-I)2Pb(TPT)] 1 (TPT is the abbreviation of 3,5,6-tris(2-pyridyl)-1,2,4-triazine ligand) has been synthesized and characterized by elemental analysis, IR, 1HNMR spectroscopy and studied by thermal and electrochemical properties as well as X-ray crystallography. The single-crystal X-ray data show two different kinds of Pb2+ ions in 1 with coordination numbers of six, Pb1=PbI6, and five, Pb2=PbN3I2, with holodirected and hemidirected coordination spheres, respectively. The supramolecular features in 1 are negotiated through the weak but directional Pb…I, C-H…N and C-H…I interactions and aromatic π-π stacking interactions.
2014, 33(8): 1191-1198
Abstract:
Reactions of Zn(NO3)2·6H2O and MNO3 (M=Na, K and Rb) with H2mip (H2mip=5-methylisophthalic acid) in DMF (DMF=N,N'-dimethylformamide) resulted in the formation of novel heterometallic metal-organic frameworks (Me2NH2)[ZnM(mip)2] (1: M=Na; 2: M=K; 3: M=Rb, mip=5-methylisophthalate dianion for 1~3). These complexes belong to the monoclinic system, space group P2/c and have been fully characterized by satisfactory elemental analysis, FT-IR spectra, TGA and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies reveal that 1~3 are 3D isomorphic structures based on a trinuclear unit {ZnM2(μ2-COO)2(μ3-COO)2} and exhibit pcu topological net and blue fluorescence.
Reactions of Zn(NO3)2·6H2O and MNO3 (M=Na, K and Rb) with H2mip (H2mip=5-methylisophthalic acid) in DMF (DMF=N,N'-dimethylformamide) resulted in the formation of novel heterometallic metal-organic frameworks (Me2NH2)[ZnM(mip)2] (1: M=Na; 2: M=K; 3: M=Rb, mip=5-methylisophthalate dianion for 1~3). These complexes belong to the monoclinic system, space group P2/c and have been fully characterized by satisfactory elemental analysis, FT-IR spectra, TGA and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies reveal that 1~3 are 3D isomorphic structures based on a trinuclear unit {ZnM2(μ2-COO)2(μ3-COO)2} and exhibit pcu topological net and blue fluorescence.
2014, 33(8): 1199-1206
Abstract:
A novel metal-organic framework, namely [Zn(C20H13O5P)]n (1), has been hydrothermally synthesized through the reaction of 5-(oxidediphenylphosphino)isophthalic acid (H2L) with Zn(Ⅱ) salt. The title compound crystallizes in monoclinic, space group P21/c with a=11.0966(10), b=14.5651(14), c=14.7311(15) Å, β=130.022(6)°, C20H13O5PZn, Mr=429.64, V=1823.3(3) Å3, Dc=1.565 g/cm3, F(000)=872, μ=1.463 mm-1, S=1.054 and Z=4. The final R=0.0270 and wR=0.0739 for 2769 observed reflections with I>2σ(I). In the title complex, the Zn2(CO2)2 binuclear clusters are linked by L2- ligands to result in a pillared layer structure in the bc plane, which is a (4,4)-net composed of helical chains with opposite chirality by sharing Zn2(CO2)2 units. Adjacent layers are further associated together through Zn-O bonds involving the metal center and the oxygen atom of P=O group to achieve a 3D architecture, in which one-dimensional quadrangled channel displays the interweaving of two pairs of coaxial double-helical chains with opposite chirality. The luminescence property and thermogravimetric analysis of the title complex were investigated.
A novel metal-organic framework, namely [Zn(C20H13O5P)]n (1), has been hydrothermally synthesized through the reaction of 5-(oxidediphenylphosphino)isophthalic acid (H2L) with Zn(Ⅱ) salt. The title compound crystallizes in monoclinic, space group P21/c with a=11.0966(10), b=14.5651(14), c=14.7311(15) Å, β=130.022(6)°, C20H13O5PZn, Mr=429.64, V=1823.3(3) Å3, Dc=1.565 g/cm3, F(000)=872, μ=1.463 mm-1, S=1.054 and Z=4. The final R=0.0270 and wR=0.0739 for 2769 observed reflections with I>2σ(I). In the title complex, the Zn2(CO2)2 binuclear clusters are linked by L2- ligands to result in a pillared layer structure in the bc plane, which is a (4,4)-net composed of helical chains with opposite chirality by sharing Zn2(CO2)2 units. Adjacent layers are further associated together through Zn-O bonds involving the metal center and the oxygen atom of P=O group to achieve a 3D architecture, in which one-dimensional quadrangled channel displays the interweaving of two pairs of coaxial double-helical chains with opposite chirality. The luminescence property and thermogravimetric analysis of the title complex were investigated.
2014, 33(8): 1207-1214
Abstract:
Reaction of ZnCl2 and 4-amino-3,5-propyl-1,2,4-triazole (dpatrz) or CdCl2, NaN3 and dpatrz, in aqueous solution at room temperature yields two neutral clusters: a dinuclear complex [Zn2(dpatrz)2Cl4] (I) and a linear trinuclear complex, [Cd3(dpatrz)4(N3)2Cl4] (Ⅱ). Both complexes have been characterized by X-ray single-crystal diffraction, powder XRD, IR, elemental analysis, TG and fluorescence analysis. Complex I crystallizes in orthorhombic, space group Pbca with a=11.865(2), b=14.464(3), c=15.985(3) Å, V=2743.4(9) Å3, Z=4, C16H32N8Cl4Zn2, Mr=609.4, Dc=1.475 g·cm3, μ=2.16 mm-1, F(000)=1248, GOOF=1.091, the final R=0.0295 and wR=0.0665 for 1999 observed reflections (I>2σ(I)). Complex Ⅱ crystallizes in monoclinic, space group P21/c with a=11.408(2), b=15.211(3), c=18.152(6) Å, β=123.75(2)°, V=2619.1(1) Å3, Z=2, C32H64N22Cl4Cd3, Mr=1236.05, Dc=1.567 g·cm3, μ=1.46 mm-1, F(000)=1244, GOOF=1.042, the final R=0.0444 and wR=0.0913 for 3466 observed reflections (I>2σ(I)). The analysis of X-ray revealed that both structures lie about the inversion centers: complex I adopts two μ1,2-triazole bridges linking two Zn(Ⅱ) ions and Ⅱ forms a linear trinuclear structure with four μ1,2-triazoles and two μ1,1-N3- bridging modes. There are different coordinated geometries for three Cd(Ⅱ) ions in Ⅱ: one is coordinated with an octahedral environment, and the other two are distorted tetragonal pyramids (τ=0.34). The hydrogen bonds of C-H…Cl and N-H…Cl lead to the discretes into a 3D supramolecular network in both compounds. The thermal stabilities and photoluminescence behaviors of them were also studied.
Reaction of ZnCl2 and 4-amino-3,5-propyl-1,2,4-triazole (dpatrz) or CdCl2, NaN3 and dpatrz, in aqueous solution at room temperature yields two neutral clusters: a dinuclear complex [Zn2(dpatrz)2Cl4] (I) and a linear trinuclear complex, [Cd3(dpatrz)4(N3)2Cl4] (Ⅱ). Both complexes have been characterized by X-ray single-crystal diffraction, powder XRD, IR, elemental analysis, TG and fluorescence analysis. Complex I crystallizes in orthorhombic, space group Pbca with a=11.865(2), b=14.464(3), c=15.985(3) Å, V=2743.4(9) Å3, Z=4, C16H32N8Cl4Zn2, Mr=609.4, Dc=1.475 g·cm3, μ=2.16 mm-1, F(000)=1248, GOOF=1.091, the final R=0.0295 and wR=0.0665 for 1999 observed reflections (I>2σ(I)). Complex Ⅱ crystallizes in monoclinic, space group P21/c with a=11.408(2), b=15.211(3), c=18.152(6) Å, β=123.75(2)°, V=2619.1(1) Å3, Z=2, C32H64N22Cl4Cd3, Mr=1236.05, Dc=1.567 g·cm3, μ=1.46 mm-1, F(000)=1244, GOOF=1.042, the final R=0.0444 and wR=0.0913 for 3466 observed reflections (I>2σ(I)). The analysis of X-ray revealed that both structures lie about the inversion centers: complex I adopts two μ1,2-triazole bridges linking two Zn(Ⅱ) ions and Ⅱ forms a linear trinuclear structure with four μ1,2-triazoles and two μ1,1-N3- bridging modes. There are different coordinated geometries for three Cd(Ⅱ) ions in Ⅱ: one is coordinated with an octahedral environment, and the other two are distorted tetragonal pyramids (τ=0.34). The hydrogen bonds of C-H…Cl and N-H…Cl lead to the discretes into a 3D supramolecular network in both compounds. The thermal stabilities and photoluminescence behaviors of them were also studied.
2014, 33(8): 1215-1221
Abstract:
Two binuclear silver complexes, [Ag2{μ-S2P(OCH2Ph)2}2(phen)2] (1) and [Ag2{μ-S2P(OCH2CH2Ph)2}2(phen)2] (2), were synthesized and characterized by elemental analysis, infrared spectrum, thermo-gravimetric analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in the triclinic system, space group P1 with a=9.7881(4), b=10.7726(4), c=13.1952(6) Å, α=103.686(4), β=99.477(3), γ=107.494(4)°, V=1246.88(9) Å3, Dc=1.591 g·m-3 and Z=1; Complex 2 is of monoclinic system, space group P21/n with a=10.6014(8), b=24.3969(15), c=11.5353(10) Å, β=14.125(10)°, V=2722.9(4) Å3, Dc=1.526 g·m-3 and Z=2. In the molecules of 1 and 2, O,O'-dialkyldithiophosphate anions, (PhCH2O)PS2- and (PhCH2CH2O)PS2- act as bridging ligands and connect two Ag(I) centers into a binuclear unit with Ag2S4P2 eight-membered rings in "chair" conformations. In both crystal structures, face-to-face π-π stacking interactions between the adjacent paralleling aromatic rings of 1,10-phenanthroline play a prominent role in the crystal packing and result in a 1D chain. And such 1D chains are further linked into 3D networks by weak intermolecular C-H…π interactions for 1.
Two binuclear silver complexes, [Ag2{μ-S2P(OCH2Ph)2}2(phen)2] (1) and [Ag2{μ-S2P(OCH2CH2Ph)2}2(phen)2] (2), were synthesized and characterized by elemental analysis, infrared spectrum, thermo-gravimetric analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in the triclinic system, space group P1 with a=9.7881(4), b=10.7726(4), c=13.1952(6) Å, α=103.686(4), β=99.477(3), γ=107.494(4)°, V=1246.88(9) Å3, Dc=1.591 g·m-3 and Z=1; Complex 2 is of monoclinic system, space group P21/n with a=10.6014(8), b=24.3969(15), c=11.5353(10) Å, β=14.125(10)°, V=2722.9(4) Å3, Dc=1.526 g·m-3 and Z=2. In the molecules of 1 and 2, O,O'-dialkyldithiophosphate anions, (PhCH2O)PS2- and (PhCH2CH2O)PS2- act as bridging ligands and connect two Ag(I) centers into a binuclear unit with Ag2S4P2 eight-membered rings in "chair" conformations. In both crystal structures, face-to-face π-π stacking interactions between the adjacent paralleling aromatic rings of 1,10-phenanthroline play a prominent role in the crystal packing and result in a 1D chain. And such 1D chains are further linked into 3D networks by weak intermolecular C-H…π interactions for 1.
2014, 33(8): 1222-1226
Abstract:
A new Zn(Ⅱ) coordination polymer, namely [Zn(Htci)(bib)0.5(H2O)]n·nH2O (1, H3tci=tri(2-carboxyethyl)isocyanurate, bib=1,4-bis(imidazol-1-ylmethyl)-butane) has been synthesized by combining H3tci and bib ligands with Zn(Ⅱ) salts under solvothermal conditions. The title compound crystallizes in monoclinic, space group P21/c with a=13.3424(7), b=7.9051(5), c=20.4650(12) Å, β=101.935(5)°, V=2111.8(2) Å3, C17H24N5O11Zn, Mr=539.8, Z=4, Dc=1.698 g/cm3, F(000)=1116, μ=1.236 mm-1, the final R=0.0398 and wR=0.00879 for 3722 observed reflections (I>2σ(I)). X-ray structural analysis reveals that compound 1 exhibits a three-dimensional (3D) pillar-layered framework, and can be simplified into a 5-connected bnn topological network. Moreover, the luminescent properties for compound 1 were also studied at room temperature.
A new Zn(Ⅱ) coordination polymer, namely [Zn(Htci)(bib)0.5(H2O)]n·nH2O (1, H3tci=tri(2-carboxyethyl)isocyanurate, bib=1,4-bis(imidazol-1-ylmethyl)-butane) has been synthesized by combining H3tci and bib ligands with Zn(Ⅱ) salts under solvothermal conditions. The title compound crystallizes in monoclinic, space group P21/c with a=13.3424(7), b=7.9051(5), c=20.4650(12) Å, β=101.935(5)°, V=2111.8(2) Å3, C17H24N5O11Zn, Mr=539.8, Z=4, Dc=1.698 g/cm3, F(000)=1116, μ=1.236 mm-1, the final R=0.0398 and wR=0.00879 for 3722 observed reflections (I>2σ(I)). X-ray structural analysis reveals that compound 1 exhibits a three-dimensional (3D) pillar-layered framework, and can be simplified into a 5-connected bnn topological network. Moreover, the luminescent properties for compound 1 were also studied at room temperature.
2014, 33(8): 1227-1233
Abstract:
The crystal structure of a solid electrolyte, beta-Al2O3, was investigated by XRD analysis and demonstrated by Diamond software. Its chemical formula was verified by the Ag ion molten salt exchange method and X-ray fluorescence analysis (XRF). The chemical formula of β-Al2O3 is Na2O·8.52Al2O3, and its crystal is of hexagonal, space group P63/mmc, with a=5.5941 Å and c=22.5300 Å. The chemical formula of β"-Al2O is Na2O·6.03Al2O3, and its crystal is of trigonal, space group R3 m, with a=5.6017 Å and c=33.6219 Å. The maximum span in the sodion migration of β"-phase (2.4283 Å) is only about a third of that for the β"-phase (6.9037 Å), so the β"-phase has higher ionic conductivity than the β-phase.
The crystal structure of a solid electrolyte, beta-Al2O3, was investigated by XRD analysis and demonstrated by Diamond software. Its chemical formula was verified by the Ag ion molten salt exchange method and X-ray fluorescence analysis (XRF). The chemical formula of β-Al2O3 is Na2O·8.52Al2O3, and its crystal is of hexagonal, space group P63/mmc, with a=5.5941 Å and c=22.5300 Å. The chemical formula of β"-Al2O is Na2O·6.03Al2O3, and its crystal is of trigonal, space group R3 m, with a=5.6017 Å and c=33.6219 Å. The maximum span in the sodion migration of β"-phase (2.4283 Å) is only about a third of that for the β"-phase (6.9037 Å), so the β"-phase has higher ionic conductivity than the β-phase.
2014, 33(8): 1234-1238
Abstract:
The subsolidus phase relationships of the system TiO2-NiO-WO3 were investigated, aiming at exploring new potential visible-light active photocatalysis systems. After the solid-state chemistry reaction in air between 1000 and 1150℃, X-ray diffraction (XRD) data showed that two binary compounds and three ternary-phase regions were contained in this ternary system. No new ternary compound was discovered under our experiment conditions. None of these phases in this system revealed a remarkable homogeneity range.
The subsolidus phase relationships of the system TiO2-NiO-WO3 were investigated, aiming at exploring new potential visible-light active photocatalysis systems. After the solid-state chemistry reaction in air between 1000 and 1150℃, X-ray diffraction (XRD) data showed that two binary compounds and three ternary-phase regions were contained in this ternary system. No new ternary compound was discovered under our experiment conditions. None of these phases in this system revealed a remarkable homogeneity range.
2014, 33(8): 1239-1244
Abstract:
Researches on α-cyanostilbene derivatives demonstrated them to be promising AIE or AIEE structural molecules and potential photoelectric materials. One novel α-cyanostilbene derivative, namely (E)-2-(4-butoxyphenyl)-3-(4-(diethylamino)phenyl)acrylonitrile (BPDPA), has been designed, synthesized and characterized. The crystalline structure of BPDPA has been studied in detail. The single-crystal X-ray diffraction revealed BPDPA crystallizes in triclinic space group P1, with a=12.860(5), b=13.327(5), c=15.016(5) Å, α=72.650(5), β=66.969(5), γ=62.897(5)°, Mr=696.95, V=2085.6(13) Å3, Z=2, Dc=1.110 g/cm-3, μ=0.068 mm-1, F(000)=752, Rint=0.0264, R(I>2σ(I))=0.0649, wR (I>2σ(I)=0.1724, R(all data)=0.1321, wR(all data)=0.2158, completeness to theta=25.00 is 99.4% and GOF=1.067. Like most reported α-cyanostilbene derivatives, BPDPA possesses a somewhat twisted molecular structure. UV-Vis and FL measurements showed an obviously bathochromic effect of BPDPA with increasing the polarity of the solvents.
Researches on α-cyanostilbene derivatives demonstrated them to be promising AIE or AIEE structural molecules and potential photoelectric materials. One novel α-cyanostilbene derivative, namely (E)-2-(4-butoxyphenyl)-3-(4-(diethylamino)phenyl)acrylonitrile (BPDPA), has been designed, synthesized and characterized. The crystalline structure of BPDPA has been studied in detail. The single-crystal X-ray diffraction revealed BPDPA crystallizes in triclinic space group P1, with a=12.860(5), b=13.327(5), c=15.016(5) Å, α=72.650(5), β=66.969(5), γ=62.897(5)°, Mr=696.95, V=2085.6(13) Å3, Z=2, Dc=1.110 g/cm-3, μ=0.068 mm-1, F(000)=752, Rint=0.0264, R(I>2σ(I))=0.0649, wR (I>2σ(I)=0.1724, R(all data)=0.1321, wR(all data)=0.2158, completeness to theta=25.00 is 99.4% and GOF=1.067. Like most reported α-cyanostilbene derivatives, BPDPA possesses a somewhat twisted molecular structure. UV-Vis and FL measurements showed an obviously bathochromic effect of BPDPA with increasing the polarity of the solvents.
2014, 33(8): 1245-1252
Abstract:
In order to study the effects of different extraction methods on the molar mass distribution and chain conformation of Fortunella margarita (Lour.) Swingle polysaccharides (FP), we used extraction by hot water (WFP), ultrasonic-assisted treatment (UFP), microwave-assisted treatment (MFP) and ultrasonic/microwave-assisted treatment (UMFP), and then Fourier transform infrared (FT-IR) spectroscopy as well as 1H and 13C nuclear magnetic resonance (NMR) spectroscopy to characterize the structural properties of FP extracted. The molar weight (Mw), polydispersity index (Mw/Mn), root-mean-square (RMS) turning radius (Rg), molar mass distribution and chain conformation of FP were studied systematically using size-exclusion chromatography (SEC), multi-angle laser light-scattering (MALLS) and refractive index (RI). WFP, UFP, MFP and UMFP are all typical carbohydrates according to 1H NMR, 13C NMR and FT-IR measurements. The type of glycosidic linkage is mainly a β-glycosidic bond with a small amount of α-glycosidic bond. The results obtained by the SEC-MALLS-RI system showed the molar masses of WFP and UMFP were distributed mainly in the range of 5.0×106~1.0×107 g·mol-1 and they accounted for 57.80% and 56.84% of total FP, respectively. The molar masses of UFP and MFP were distributed mainly in the 1.0×106~5.0×106 g·mol-1 range, which accounted for 38.24% and 52.39% of FP, respectively. WFP and UMFP in water were uniform spherical polymers; UFP and MFP were typical highly branched polymers and the degree of branching for MFP was higher compared to UFP. These results indicated the ultrasonic- and microwave-assisted extraction methods caused a significant decrease of the molar mass of FP but the ultrasonic/microwave synergistic extraction method had no effect.
In order to study the effects of different extraction methods on the molar mass distribution and chain conformation of Fortunella margarita (Lour.) Swingle polysaccharides (FP), we used extraction by hot water (WFP), ultrasonic-assisted treatment (UFP), microwave-assisted treatment (MFP) and ultrasonic/microwave-assisted treatment (UMFP), and then Fourier transform infrared (FT-IR) spectroscopy as well as 1H and 13C nuclear magnetic resonance (NMR) spectroscopy to characterize the structural properties of FP extracted. The molar weight (Mw), polydispersity index (Mw/Mn), root-mean-square (RMS) turning radius (Rg), molar mass distribution and chain conformation of FP were studied systematically using size-exclusion chromatography (SEC), multi-angle laser light-scattering (MALLS) and refractive index (RI). WFP, UFP, MFP and UMFP are all typical carbohydrates according to 1H NMR, 13C NMR and FT-IR measurements. The type of glycosidic linkage is mainly a β-glycosidic bond with a small amount of α-glycosidic bond. The results obtained by the SEC-MALLS-RI system showed the molar masses of WFP and UMFP were distributed mainly in the range of 5.0×106~1.0×107 g·mol-1 and they accounted for 57.80% and 56.84% of total FP, respectively. The molar masses of UFP and MFP were distributed mainly in the 1.0×106~5.0×106 g·mol-1 range, which accounted for 38.24% and 52.39% of FP, respectively. WFP and UMFP in water were uniform spherical polymers; UFP and MFP were typical highly branched polymers and the degree of branching for MFP was higher compared to UFP. These results indicated the ultrasonic- and microwave-assisted extraction methods caused a significant decrease of the molar mass of FP but the ultrasonic/microwave synergistic extraction method had no effect.
2014, 33(8): 1253-1260
Abstract:
The dynamic changes of the complex network and the material form and function were actuated by the molecular chains. The interaction behavior between molecular chains was difficult to illuminate because the dynamic changes of macromolecules were observed difficultly by normal spectrum method and the methods to test and evaluate the complex network evolution prediction and intervention are rare. The mathematic model of domino offect of molecular chains was established based on the topological structure of molecular chain aggregation of Konjac glucomannan, and the molecular entanglement mechanism of Konjac glucamannan blends was studied through molecular simulation and knot theory analysis combined with experimental verification. The results suggested that two network models (topological entanglement and solid knot) of Konjac glucomannon blends were formed through hydrogen bond nodes. The topological entanglement was strengthened with the increase of concentration and the form of molecular chains was Gaussian chain which could not allow traverse moving owing to the intermolecular cross and entanglement and the shield of intramolecular interaction. Besides, the structures of Konjac glucomannon blends became more stable due to the solid knot. Both of them were verified by the experimental results. This experimental method simplifies the microscopic description of Konjac glucomannon, and there is important guiding significance of the experimental results for the prediction and control of polysaccharides’ structure and function.
The dynamic changes of the complex network and the material form and function were actuated by the molecular chains. The interaction behavior between molecular chains was difficult to illuminate because the dynamic changes of macromolecules were observed difficultly by normal spectrum method and the methods to test and evaluate the complex network evolution prediction and intervention are rare. The mathematic model of domino offect of molecular chains was established based on the topological structure of molecular chain aggregation of Konjac glucomannan, and the molecular entanglement mechanism of Konjac glucamannan blends was studied through molecular simulation and knot theory analysis combined with experimental verification. The results suggested that two network models (topological entanglement and solid knot) of Konjac glucomannon blends were formed through hydrogen bond nodes. The topological entanglement was strengthened with the increase of concentration and the form of molecular chains was Gaussian chain which could not allow traverse moving owing to the intermolecular cross and entanglement and the shield of intramolecular interaction. Besides, the structures of Konjac glucomannon blends became more stable due to the solid knot. Both of them were verified by the experimental results. This experimental method simplifies the microscopic description of Konjac glucomannon, and there is important guiding significance of the experimental results for the prediction and control of polysaccharides’ structure and function.
