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2016 Volume 35 Issue 9
2016, 35(9): 1319-1327
doi: 10.14102/j.cnki.0254-5861.2011-1104
Abstract:
The nociceptin receptor(NOP) has been involved in multiple biological functions, including pain, anxiety, cough, substance abuse, cardiovascular control, and immunity. Thus, selective NOP agonists might have clinical potential for the treatment of related diseases. In the present work, three-dimensional quantitative structure-activity relationship(3D-QSAR) studies were performed on a series of 3-substituted N-benzhydryl-nortropane analogs as NOP agonists using comparative molecular field analysis(Co MFA) and comparative molecular similarity indices analysis(CoM SIA) techniques. The statistically significant models were obtained with 54 compounds in training set by ligand-based atom-by-atom matching alignment. The CoM FA model gave cross-validated coefficient(q2) value of 0.530 using 6 components, non-cross-validated(r2) value of 0.921 with estimated F value of 93.668, and standard error of estimate(SEE) of 0.185. The best Co MSIA model resulted in q2=0.592, r2=0.945, N=10, SEE=0.162, and F=75.654, based on steric, electrostatic, hydrophobic and hydrogen bond acceptor fields. The predictive ability of the Co MFA and CoM SIA models was further validated using a test set of 18 molecules that were not included in the training set, which resulted in predictive correlation coefficients(rpred2) of 0.551 and 0.637, respectively. Moreover, the CoM FA and CoM SIA contour maps identified the features important for exhibiting potent binding affinities on NOP, and can thus serve as a useful guide for the design of potential NOP agonists.
The nociceptin receptor(NOP) has been involved in multiple biological functions, including pain, anxiety, cough, substance abuse, cardiovascular control, and immunity. Thus, selective NOP agonists might have clinical potential for the treatment of related diseases. In the present work, three-dimensional quantitative structure-activity relationship(3D-QSAR) studies were performed on a series of 3-substituted N-benzhydryl-nortropane analogs as NOP agonists using comparative molecular field analysis(Co MFA) and comparative molecular similarity indices analysis(CoM SIA) techniques. The statistically significant models were obtained with 54 compounds in training set by ligand-based atom-by-atom matching alignment. The CoM FA model gave cross-validated coefficient(q2) value of 0.530 using 6 components, non-cross-validated(r2) value of 0.921 with estimated F value of 93.668, and standard error of estimate(SEE) of 0.185. The best Co MSIA model resulted in q2=0.592, r2=0.945, N=10, SEE=0.162, and F=75.654, based on steric, electrostatic, hydrophobic and hydrogen bond acceptor fields. The predictive ability of the Co MFA and CoM SIA models was further validated using a test set of 18 molecules that were not included in the training set, which resulted in predictive correlation coefficients(rpred2) of 0.551 and 0.637, respectively. Moreover, the CoM FA and CoM SIA contour maps identified the features important for exhibiting potent binding affinities on NOP, and can thus serve as a useful guide for the design of potential NOP agonists.
2016, 35(9): 1328-1338
doi: 10.14102/j.cnki.0254-5861.2011-1152
Abstract:
Pt-TiO2 nanotubes with tube diameter of ~120 nm and uniformly dispersed Pt particles(size of ~2 nm) were successfully synthesized via a carbon nanotube(CNT) templating method followed by a photo-deposition processing of Pt nanoparticles. The as-obtained Pt-TiO2 NTs possess both enhanced visible light absorption and reduced recombination of photogenerated electrons and holes. These merits boost the Pt-TiO2 NTs an excellent photocatalytic material toward photooxidation of a variety of low molecular hydrocarbons under atmospheric environment.
Pt-TiO2 nanotubes with tube diameter of ~120 nm and uniformly dispersed Pt particles(size of ~2 nm) were successfully synthesized via a carbon nanotube(CNT) templating method followed by a photo-deposition processing of Pt nanoparticles. The as-obtained Pt-TiO2 NTs possess both enhanced visible light absorption and reduced recombination of photogenerated electrons and holes. These merits boost the Pt-TiO2 NTs an excellent photocatalytic material toward photooxidation of a variety of low molecular hydrocarbons under atmospheric environment.
2016, 35(9): 1339-1347
doi: 10.14102/j.cnki.0254-5861.2011-1009
Abstract:
This study presents the interaction between konjac glucanmannan(KGM) and cationic surfactant dodecyl trimethylammonium chloride(DTAC) to provide theoretical guidance and prediction for the experimental design and application of this composite system. Dissipative particle dynamics(DPD) method was used to simulate the interaction between KGM and the cationic surfactant. Influences of concentration, temperature and shear process on the structure and properties of aggregates were mainly examined. The results revealed that the density peak increased with the increase of concentration of KGM. With increasing the temperature, density peak moved to the right and increased, and then decreased when the temperature rose to a certain value. The density peak moved to the right at the low shear rate while decreased at the high one. During simulation, the high viscosity related to the low diffusion rate, which made it difficult to form a large continuous phase.
This study presents the interaction between konjac glucanmannan(KGM) and cationic surfactant dodecyl trimethylammonium chloride(DTAC) to provide theoretical guidance and prediction for the experimental design and application of this composite system. Dissipative particle dynamics(DPD) method was used to simulate the interaction between KGM and the cationic surfactant. Influences of concentration, temperature and shear process on the structure and properties of aggregates were mainly examined. The results revealed that the density peak increased with the increase of concentration of KGM. With increasing the temperature, density peak moved to the right and increased, and then decreased when the temperature rose to a certain value. The density peak moved to the right at the low shear rate while decreased at the high one. During simulation, the high viscosity related to the low diffusion rate, which made it difficult to form a large continuous phase.
2016, 35(9): 1348-1354
doi: 10.14102/j.cnki.0254-5861.2011-1203
Abstract:
The crystal structure of the new cinnamide derivative(E)-1-(4-(4-chlorobenzyl) piperazin-1-yl)-3-(benzo[d] [1,3]dioxol-5-yl) prop-2-en-1-one(C21H21ClN2O3, Mr=384.85) was determined by single-crystal X-ray diffraction method. Compound 5 crystallizes in the monoclinic system, space group P21/c with a=11.762(2), b=15.279(3), c=11.865(2)Å, β=116.57(3)°, V=1907.1(7)Å3, Z=4, Dc=1.340 g/cm3, F(000)=808, μ=0.224 mm-1, MoKα radiation(λ=0.71073Å), the final R=0.0565 and wR=0.1479 for 2318 observed reflections with I>2σ(I). Intramolecular C(9)-H(9A)…O(1) interactions as well as intermolecular C(16)-H(16A)…O(1) hydrogen bonds help to stabilize the crystal structure. The bioassay results indicated that the title compound displayed promising neuroprotection in vitro and in vivo, and suppressed apoptosis of glutamate-induced PC12 cells.
The crystal structure of the new cinnamide derivative(E)-1-(4-(4-chlorobenzyl) piperazin-1-yl)-3-(benzo[d] [1,3]dioxol-5-yl) prop-2-en-1-one(C21H21ClN2O3, Mr=384.85) was determined by single-crystal X-ray diffraction method. Compound 5 crystallizes in the monoclinic system, space group P21/c with a=11.762(2), b=15.279(3), c=11.865(2)Å, β=116.57(3)°, V=1907.1(7)Å3, Z=4, Dc=1.340 g/cm3, F(000)=808, μ=0.224 mm-1, MoKα radiation(λ=0.71073Å), the final R=0.0565 and wR=0.1479 for 2318 observed reflections with I>2σ(I). Intramolecular C(9)-H(9A)…O(1) interactions as well as intermolecular C(16)-H(16A)…O(1) hydrogen bonds help to stabilize the crystal structure. The bioassay results indicated that the title compound displayed promising neuroprotection in vitro and in vivo, and suppressed apoptosis of glutamate-induced PC12 cells.
2016, 35(9): 1355-1361
doi: 10.14102/j.cnki.0254-5861.2011-1096
Abstract:
Based on the density functional theory with generalized gradient approximation, the stable geometrical structures of one or more CO molecules adsorbed on the Al6Si cluster are investigated and the corresponding adsorption energies are also calculated. It is found that the cluster Al6Si can adsorb six CO molecules. The thermal stability of the (CO)6@Al6Si complexes is examined using the atom centered density matrix propagation molecular dynamics calculations at 373 K. The results show that two isomers of Al6Si cluster can solidly adsorb six CO molecules, and the other isomer adsorbs four ones. Therefore, the Al6Si cluster is a promising candidate for eliminating CO effectively.
Based on the density functional theory with generalized gradient approximation, the stable geometrical structures of one or more CO molecules adsorbed on the Al6Si cluster are investigated and the corresponding adsorption energies are also calculated. It is found that the cluster Al6Si can adsorb six CO molecules. The thermal stability of the (CO)6@Al6Si complexes is examined using the atom centered density matrix propagation molecular dynamics calculations at 373 K. The results show that two isomers of Al6Si cluster can solidly adsorb six CO molecules, and the other isomer adsorbs four ones. Therefore, the Al6Si cluster is a promising candidate for eliminating CO effectively.
2016, 35(9): 1362-1368
doi: 10.14102/j.cnki.0254-5861.2011-1106
Abstract:
A novel D-π-A type α-cyanostilbenzene derivative,(Z)-2-(4-aminophenyl)-3-(4-bromophenyl)-acrylonitrile(ABAN), was designed and synthesized, by introducing an electrondonating amino group and a heavy atom. The structure of ABAN was confirmed by FT-IR, 1H NMR, 13C NMR spectra and single-crystal X-ray diffraction analysis. The ABAN is of orthorhombic system, space group P212121, with a=8.6100(14), b=9.6923(16), c=15.705(3)Å, Mr=299.17, V=1310.6(4)Å3, Z=4, Dc=1.516 g/cm-3, μ=3.119 mm-1, F(000)=600, Rint=0.038, R(I>2σ(I))=0.0276, wR(I>2σ(I))=0.0628, R(all data)=0.0324, wR(all data)=0.0646, completeness to theta=25.00 was 99.8% and GOOF=1.04. In the crystal structure, ABAN molecules were linked with each other through intermolecular C-H…π interactions and N-H…N hydrogen bonds, by which the 1D chain, 2D plane and 3D stacking structures were constructed. The photophysical properties and calculation results confirmed that ABAN possessed an intramolecular charge transfer(ICT) process. ABAN could be applied into the optoelectronic material field due to good solvent-tuned photophysical properties and highly thermal stability.
A novel D-π-A type α-cyanostilbenzene derivative,(Z)-2-(4-aminophenyl)-3-(4-bromophenyl)-acrylonitrile(ABAN), was designed and synthesized, by introducing an electrondonating amino group and a heavy atom. The structure of ABAN was confirmed by FT-IR, 1H NMR, 13C NMR spectra and single-crystal X-ray diffraction analysis. The ABAN is of orthorhombic system, space group P212121, with a=8.6100(14), b=9.6923(16), c=15.705(3)Å, Mr=299.17, V=1310.6(4)Å3, Z=4, Dc=1.516 g/cm-3, μ=3.119 mm-1, F(000)=600, Rint=0.038, R(I>2σ(I))=0.0276, wR(I>2σ(I))=0.0628, R(all data)=0.0324, wR(all data)=0.0646, completeness to theta=25.00 was 99.8% and GOOF=1.04. In the crystal structure, ABAN molecules were linked with each other through intermolecular C-H…π interactions and N-H…N hydrogen bonds, by which the 1D chain, 2D plane and 3D stacking structures were constructed. The photophysical properties and calculation results confirmed that ABAN possessed an intramolecular charge transfer(ICT) process. ABAN could be applied into the optoelectronic material field due to good solvent-tuned photophysical properties and highly thermal stability.
2016, 35(9): 1369-1375
doi: 10.14102/j.cnki.0254-5861.2011-1131
Abstract:
One new quaternary rare-earth sulfide, FeSm6Si2S14, has been synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the noncentrosymmetric hexagonal space group P63, belonging to the Ce6Al3.33S14 structure-type, and the AxRE3MQ7 family. Its crystal structure features a 3-D framework constructed by SmS8 bicapped trigonal prisms, where Fe and Si atoms occupy the octahedral(2a) and tetrahedral(2c) voids, respectively. The FeS6 octahedra are connected with each other to form a chain along the b direction. FeSm6Si2S14 represents a new chemical composition among the large family of AxRE3MQ7 compounds. The other related compounds containing transition metal are also discussed.
One new quaternary rare-earth sulfide, FeSm6Si2S14, has been synthesized by a facile solid-state route with boron as the reducing reagent. It crystallizes in the noncentrosymmetric hexagonal space group P63, belonging to the Ce6Al3.33S14 structure-type, and the AxRE3MQ7 family. Its crystal structure features a 3-D framework constructed by SmS8 bicapped trigonal prisms, where Fe and Si atoms occupy the octahedral(2a) and tetrahedral(2c) voids, respectively. The FeS6 octahedra are connected with each other to form a chain along the b direction. FeSm6Si2S14 represents a new chemical composition among the large family of AxRE3MQ7 compounds. The other related compounds containing transition metal are also discussed.
2016, 35(9): 1376-1382
doi: 10.14102/j.cnki.0254-5861.2011-1084
Abstract:
One new polymer[Co(L)(H2O)2]n(1) was synthesized by 4-(ethoxycarbonyl)-5-methyl-1H-1,2,3-triazole-1-carboxylic acid(Emtc) under the in situ solvent thermal reaction(H2L=1-(carboxymethyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid). The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η2:η1η1:η1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.
One new polymer[Co(L)(H2O)2]n(1) was synthesized by 4-(ethoxycarbonyl)-5-methyl-1H-1,2,3-triazole-1-carboxylic acid(Emtc) under the in situ solvent thermal reaction(H2L=1-(carboxymethyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid). The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η2:η1η1:η1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.
2016, 35(9): 1383-1390
doi: 10.14102/j.cnki.0254-5861.2011-1075
Abstract:
A series of isostructural d/f molecular compounds Zn(H2L) Ln(NO3)3·CH3OH(Ln=Dy(1), Tb(2) and Sm(3)) were synthesized by the introduction of a designed multifunctional ligand N,N',N'',N'''-tetra(2-hydroxy-3-methoxy-5-methylbenzyl)-1,4,7,10-tetraazacyclododecan(H4L=C44H60N4O8). In the isostructural molecules, each crystallographically independent Zn2+ and Ln3+ centers are connected by two phenolic oxygen atoms. For the six-coordinate Zn2+ ion, the coordination geometry can be viewed as a regular bicapped square pyramid. While for the ten-coordinate Ln3+ ion, if each O,O'-chelated nitrate ligand is seen as a single coordination site, the coordination geometry can be viewed as a distorted pentagonal bipyramid. The fluorescent spectra show that compounds 2 and 3 exhibited characteristic sharp emissions of Tb3+ and Sm3+, respectively, while compound 1 was found to be a single-component white-light-emitting complex in the solid state. Thermal stabilities of the three compounds were investigated by using thermal gravimetric analysis. In addition, the thermal decomposition of compound 1 was confirmed by temperature-dependent powder X-ray diffraction technique.
A series of isostructural d/f molecular compounds Zn(H2L) Ln(NO3)3·CH3OH(Ln=Dy(1), Tb(2) and Sm(3)) were synthesized by the introduction of a designed multifunctional ligand N,N',N'',N'''-tetra(2-hydroxy-3-methoxy-5-methylbenzyl)-1,4,7,10-tetraazacyclododecan(H4L=C44H60N4O8). In the isostructural molecules, each crystallographically independent Zn2+ and Ln3+ centers are connected by two phenolic oxygen atoms. For the six-coordinate Zn2+ ion, the coordination geometry can be viewed as a regular bicapped square pyramid. While for the ten-coordinate Ln3+ ion, if each O,O'-chelated nitrate ligand is seen as a single coordination site, the coordination geometry can be viewed as a distorted pentagonal bipyramid. The fluorescent spectra show that compounds 2 and 3 exhibited characteristic sharp emissions of Tb3+ and Sm3+, respectively, while compound 1 was found to be a single-component white-light-emitting complex in the solid state. Thermal stabilities of the three compounds were investigated by using thermal gravimetric analysis. In addition, the thermal decomposition of compound 1 was confirmed by temperature-dependent powder X-ray diffraction technique.
2016, 35(9): 1391-1398
doi: 10.14102/j.cnki.0254-5861.2011-1089
Abstract:
A new metal-organic coordination polymer {[Nd(tci)(H2O)2]·2H2O}n(1) has been synthesized based on the flexible tricarboxylate ligand tris(2-carboxyethyl) isocyanuric acid(H3tci) and structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, infrared spectra(IR), powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). Complex 1 crystallizes in triclinic, space group P1 with a=9.1648(11), b=9.3326(12), c=12.440(2)Å, C12H20N3O13 Nd, Mr=558.55, V=886.9(2)Å3, Z=2, Dc=2.092 g·cm-3, μ=3.006 mm-1, F(000)=554, 2.56 < θ < 25.00°, λ(MoKα)=0.71073Å, T=293(2) K, the final R=0.0662 and wR=0.2071. X-ray diffraction analysis reveals that complex 1 is a two-dimensional layer, which is further assembled into a three-dimensional supramolecular architecture through hydrogen bonding interactions. The structure of complex 1 can be simplified as a rare 2-periodic uninodal {48·62} topology and a non-interpenetrating kgd topology. Furthermore, the thermal stability and photoluminescence property of 1 were investigated.
A new metal-organic coordination polymer {[Nd(tci)(H2O)2]·2H2O}n(1) has been synthesized based on the flexible tricarboxylate ligand tris(2-carboxyethyl) isocyanuric acid(H3tci) and structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, infrared spectra(IR), powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). Complex 1 crystallizes in triclinic, space group P1 with a=9.1648(11), b=9.3326(12), c=12.440(2)Å, C12H20N3O13 Nd, Mr=558.55, V=886.9(2)Å3, Z=2, Dc=2.092 g·cm-3, μ=3.006 mm-1, F(000)=554, 2.56 < θ < 25.00°, λ(MoKα)=0.71073Å, T=293(2) K, the final R=0.0662 and wR=0.2071. X-ray diffraction analysis reveals that complex 1 is a two-dimensional layer, which is further assembled into a three-dimensional supramolecular architecture through hydrogen bonding interactions. The structure of complex 1 can be simplified as a rare 2-periodic uninodal {48·62} topology and a non-interpenetrating kgd topology. Furthermore, the thermal stability and photoluminescence property of 1 were investigated.
A Novel TADDOL-based Chiral Metal-organic Framework:Synthesis, Structure and Photoluminescence Study
2016, 35(9): 1399-1405
doi: 10.14102/j.cnki.0254-5861.2011-1093
Abstract:
A new C2-symmetric TADDOL-based ligand H4L was designed and synthesized from readily available tartaric acid and was used to construct a novel TADDOL-based chiral metal-organic framework {[Co2L(DMA)(H2O)5]·2DMA}n 1(DMA=N,N'-dimethylacetamide). It was characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra(FTIR), solid-state circular dichroism(CD) and thermal gravimetric analysis(TGA). 1 crystallizes in the chiral orthorhombic space group P212121 with a=9.7060(8), b=15.5661(1), c=44.564(3)Å, V=6732.9(9)Å3, Z=4, Mr=1394.08, Dc=1.375 g/cm3, F(000)=2888, GOOF=1.032, the final R=0.0607 and wR=0.1582 for 21374 observed reflections with I>2σ(I). Each Co2 cluster in 1 is linked by three ligands and each ligand is coordinated to three Co2 clusters with one free carboxylate group, thus generating a 2D network. These 2D networks are further extended into a 3D supramolecule framework by the hydrogen bonding interactions(O-H…O) in an A-B-A-B stacking mode. Additionally, the photoluminescence of 1 and H4L were also investigated.
A new C2-symmetric TADDOL-based ligand H4L was designed and synthesized from readily available tartaric acid and was used to construct a novel TADDOL-based chiral metal-organic framework {[Co2L(DMA)(H2O)5]·2DMA}n 1(DMA=N,N'-dimethylacetamide). It was characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra(FTIR), solid-state circular dichroism(CD) and thermal gravimetric analysis(TGA). 1 crystallizes in the chiral orthorhombic space group P212121 with a=9.7060(8), b=15.5661(1), c=44.564(3)Å, V=6732.9(9)Å3, Z=4, Mr=1394.08, Dc=1.375 g/cm3, F(000)=2888, GOOF=1.032, the final R=0.0607 and wR=0.1582 for 21374 observed reflections with I>2σ(I). Each Co2 cluster in 1 is linked by three ligands and each ligand is coordinated to three Co2 clusters with one free carboxylate group, thus generating a 2D network. These 2D networks are further extended into a 3D supramolecule framework by the hydrogen bonding interactions(O-H…O) in an A-B-A-B stacking mode. Additionally, the photoluminescence of 1 and H4L were also investigated.
2016, 35(9): 1406-1412
doi: 10.14102/j.cnki.0254-5861.2011-1115
Abstract:
The hydrothermal reaction of 5-methoxyisophthalic acid(MeO-H2ip), 1,3-bis(2-methylimidazol-1'-yl)propane(bmip) and Zn(NO3)2·6H2O in the presence of NaOCH3 gave rise to a three-dimensional(3-D) metal-organic framework containing octanuclear Zn(II) units,[Zn4(MeO-ip)3(OH)2(bmip)]n. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the triclinic space group P1 with a=11.348(3), b=14.163(4), c=15.088(4)Å, α=108.537(2), β=106.542(2), γ=103.106(1)°, V=2065.4(9)Å3, Z=2, Mr=334.62, Dc=1.740 g·cm-3, μ=2.375 mm-1, S=1.015, F(000)=1096, the final R=0.0272 and wR=0.0715 for 8929 observed reflections(I>2σ(I)). The complex is thermally stable up to 370℃, and exhibits photoluminescent emission at 450 nm on 350 nm excitation.
The hydrothermal reaction of 5-methoxyisophthalic acid(MeO-H2ip), 1,3-bis(2-methylimidazol-1'-yl)propane(bmip) and Zn(NO3)2·6H2O in the presence of NaOCH3 gave rise to a three-dimensional(3-D) metal-organic framework containing octanuclear Zn(II) units,[Zn4(MeO-ip)3(OH)2(bmip)]n. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the triclinic space group P1 with a=11.348(3), b=14.163(4), c=15.088(4)Å, α=108.537(2), β=106.542(2), γ=103.106(1)°, V=2065.4(9)Å3, Z=2, Mr=334.62, Dc=1.740 g·cm-3, μ=2.375 mm-1, S=1.015, F(000)=1096, the final R=0.0272 and wR=0.0715 for 8929 observed reflections(I>2σ(I)). The complex is thermally stable up to 370℃, and exhibits photoluminescent emission at 450 nm on 350 nm excitation.
2016, 35(9): 1413-1419
doi: 10.14102/j.cnki.0254-5861.2011-1124
Abstract:
By the reaction of different aromatic dicarboxylic acid with zinc nitrate, three metal-carboxylate frameworks,[Zn3(BDC)3(EtOH)2](1),[Zn3(BDC)3(py)2]·2DMF(2), and[Zn3(NH2-BDC)3(H2O)2]·5DMF(3) which are constructed on the same linear trinuclear Zn3(RCOO)6 secondary building units, have been synthesized and characterized by X-ray diffraction analyses. Structural analyses showed that there are terephthalic acids as ligand linkers to form the hxl topological layer structures for 1 and 2. The introduction of the rigid aromatic ring pyridine in 2 as the terminal co-ligand of Zn3-SBU to instead of the flexible ethanol in 1, will form the layer-pillared supramolecular systems with 2-D crisscross channels, through its π-π stacking interactions. Owing to the steric hindrance of amino groups, 3 was assembled into a three-dimensional porous structure with pcu topology derived from the 2-amino-terephthalic acid as linkers to connect the Zn3-SBUs through a head-to-tail type.
By the reaction of different aromatic dicarboxylic acid with zinc nitrate, three metal-carboxylate frameworks,[Zn3(BDC)3(EtOH)2](1),[Zn3(BDC)3(py)2]·2DMF(2), and[Zn3(NH2-BDC)3(H2O)2]·5DMF(3) which are constructed on the same linear trinuclear Zn3(RCOO)6 secondary building units, have been synthesized and characterized by X-ray diffraction analyses. Structural analyses showed that there are terephthalic acids as ligand linkers to form the hxl topological layer structures for 1 and 2. The introduction of the rigid aromatic ring pyridine in 2 as the terminal co-ligand of Zn3-SBU to instead of the flexible ethanol in 1, will form the layer-pillared supramolecular systems with 2-D crisscross channels, through its π-π stacking interactions. Owing to the steric hindrance of amino groups, 3 was assembled into a three-dimensional porous structure with pcu topology derived from the 2-amino-terephthalic acid as linkers to connect the Zn3-SBUs through a head-to-tail type.
2016, 35(9): 1420-1426
doi: 10.14102/j.cnki.0254-5861.2011-1140
Abstract:
A new one-dimensional(1D) polymer,[Zn(HMIDC)(bpy)]n·2nH2O(1, H3MIDC=2-methyl-imidazole-4,5-dicarboxylic acid, bpy=2,2'-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a=14.404(3), b=8.6900(17), c=26.570(5)Å, V=3325.8(11)Å3, Dc=1.700 g/cm3, Mr=425.70, Z=8, F(000)=1744, μ=1.522 mm-1, the final R=0.0421 and wR=0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.
A new one-dimensional(1D) polymer,[Zn(HMIDC)(bpy)]n·2nH2O(1, H3MIDC=2-methyl-imidazole-4,5-dicarboxylic acid, bpy=2,2'-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a=14.404(3), b=8.6900(17), c=26.570(5)Å, V=3325.8(11)Å3, Dc=1.700 g/cm3, Mr=425.70, Z=8, F(000)=1744, μ=1.522 mm-1, the final R=0.0421 and wR=0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.
2016, 35(9): 1427-1437
doi: 10.14102/j.cnki.0254-5861.2011-1177
Abstract:
Four types of luminescent properties of metal-organic frameworks(MOFs) with formulas[Cd(1,2-BIYB)2(H2O)2]n·n(AQ-1,5-DAD)(1),[Cd(AQ-1,5-DAD)(1,3-BIYB)2]n(2),[Cd(1,3-BIYB)]n·n(AQ-1,5-DAD)·n H2O(3), and [Zn(1,4-BIYB)2]n·n(AQ-1,5-DAD)2·6H2O(4),(Na2AQ-1,5-DAD=anthraquinone-1,5-disulfonic acid disodium, 1,2-BIYB=1,2-bis(imidazol-1-ylmethyl) benzene, 1,3-BIYB=1,3-bis(imidazol-1-ylmethyl) benzene, 1,4-BIYB=1,4-bis(imidazol-1-ylmethyl)benzene) have been synthesized based on a rare sulfonate and imidazole Co-ligand system under different conditions. The structural features of four types of MOFs 1~4 are as follows:MOFs 1 show a 3D supramolecular compound in which the double one-dimensional chains are further cross-linked by hydrogen bonds. 2 exhibits a 2D network constructed by two different 1D chains. 3 features a 2D supramolecular network, in which the 1D chains and AQ-1,5-DAD are arranged alternately through hydrogen bonds. 4 posseses a 3D supramolecular structure constructed by a 2D network and one-dimensional hydrogen bonding chains. All compounds 1~4 are characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The luminescence properties of 1~4 have been investigated.
Four types of luminescent properties of metal-organic frameworks(MOFs) with formulas[Cd(1,2-BIYB)2(H2O)2]n·n(AQ-1,5-DAD)(1),[Cd(AQ-1,5-DAD)(1,3-BIYB)2]n(2),[Cd(1,3-BIYB)]n·n(AQ-1,5-DAD)·n H2O(3), and [Zn(1,4-BIYB)2]n·n(AQ-1,5-DAD)2·6H2O(4),(Na2AQ-1,5-DAD=anthraquinone-1,5-disulfonic acid disodium, 1,2-BIYB=1,2-bis(imidazol-1-ylmethyl) benzene, 1,3-BIYB=1,3-bis(imidazol-1-ylmethyl) benzene, 1,4-BIYB=1,4-bis(imidazol-1-ylmethyl)benzene) have been synthesized based on a rare sulfonate and imidazole Co-ligand system under different conditions. The structural features of four types of MOFs 1~4 are as follows:MOFs 1 show a 3D supramolecular compound in which the double one-dimensional chains are further cross-linked by hydrogen bonds. 2 exhibits a 2D network constructed by two different 1D chains. 3 features a 2D supramolecular network, in which the 1D chains and AQ-1,5-DAD are arranged alternately through hydrogen bonds. 4 posseses a 3D supramolecular structure constructed by a 2D network and one-dimensional hydrogen bonding chains. All compounds 1~4 are characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The luminescence properties of 1~4 have been investigated.
2016, 35(9): 1438-1444
doi: 10.14102/j.cnki.0254-5861.2011-1144
Abstract:
A chiral supramolecular coordination polymer,[Co(HL)·(DMF)]n(1), with helical chains from a flexible ligand 5-(imidazol-1-ylmethyl)isophthalic acid(H2L) has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), IR, Uv/vis spectra, thermal gravimetric analyses(TGA) and also by single-crystal X-ray diffraction. It crystallizes in hexagonal, space group P6522 with a=8.8109(3), b=8.8109(3), c=71.771(3)Å, γ=120°, V=4825.3(3)Å3, Z=6, Mr=695.55, Dc=1.436 g/cm3, Rint=0.0684, F(000)=2166, the final R=0.0923 and wR=0.2697 for 3056 observed reflections(I>2σ(I)). The title coordination polymer 1 shows a chiral layered structure based on right-handed helix chains. Such layers are associated together through hydrogen-bonding interactions to form a 3D supramolecular framework.
A chiral supramolecular coordination polymer,[Co(HL)·(DMF)]n(1), with helical chains from a flexible ligand 5-(imidazol-1-ylmethyl)isophthalic acid(H2L) has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), IR, Uv/vis spectra, thermal gravimetric analyses(TGA) and also by single-crystal X-ray diffraction. It crystallizes in hexagonal, space group P6522 with a=8.8109(3), b=8.8109(3), c=71.771(3)Å, γ=120°, V=4825.3(3)Å3, Z=6, Mr=695.55, Dc=1.436 g/cm3, Rint=0.0684, F(000)=2166, the final R=0.0923 and wR=0.2697 for 3056 observed reflections(I>2σ(I)). The title coordination polymer 1 shows a chiral layered structure based on right-handed helix chains. Such layers are associated together through hydrogen-bonding interactions to form a 3D supramolecular framework.
2016, 35(9): 1445-1450
doi: 10.14102/j.cnki.0254-5861.2011-1136
Abstract:
A novel coordination polymer[Zn2(BTA)2(TDC)]n(HBTA=benzotriazole, H2TDC=thiophene-2,5-dicarboxylic acid) has been synthesized by the reaction of zinc(Ⅱ), H2TDC and HBTA. This compound is fully structurally characterized by elemental analysis, IR, and single-crystal X-ray crystallography. The bulk new materials were further identified by X-ray powder diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbcn, with a=9.8825(8), b=9.4047(8), c=20.5567(17)Å, V=1910.6(3)Å3, C18H10N6O4SZn2, Mr=537.12, Dc=1.867 g/cm3, μ(MoKα)=2.662 mm-1, F(000)=1072, Z=4, S=1.058, the final R=0.0201 and wR=0.0530 for 1700 observed reflections(I>2σ(I)). Its compositional stability and photoluminescence properties were further investigated to establish the structure-property relationships. Structural analysis reveals that this compound is a 3D(4, 4)-connected framework with the(66)(64·82) topology.
A novel coordination polymer[Zn2(BTA)2(TDC)]n(HBTA=benzotriazole, H2TDC=thiophene-2,5-dicarboxylic acid) has been synthesized by the reaction of zinc(Ⅱ), H2TDC and HBTA. This compound is fully structurally characterized by elemental analysis, IR, and single-crystal X-ray crystallography. The bulk new materials were further identified by X-ray powder diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbcn, with a=9.8825(8), b=9.4047(8), c=20.5567(17)Å, V=1910.6(3)Å3, C18H10N6O4SZn2, Mr=537.12, Dc=1.867 g/cm3, μ(MoKα)=2.662 mm-1, F(000)=1072, Z=4, S=1.058, the final R=0.0201 and wR=0.0530 for 1700 observed reflections(I>2σ(I)). Its compositional stability and photoluminescence properties were further investigated to establish the structure-property relationships. Structural analysis reveals that this compound is a 3D(4, 4)-connected framework with the(66)(64·82) topology.
2016, 35(9): 1451-1460
doi: 10.14102/j.cnki.0254-5861.2011-1123
Abstract:
Six first row transition metal complexes with 1,6-bis(2'-pyridyl)-2,5-dithiahexane(Py2S2), namely, MnPy2S2Cl2(1), FePy2S2Cl2(2), CoPy2S2Cl(3), CoPy2S2(SCN)2(4), NiPy2S2(SCN)2(5) and NiPy2S2(N3)2(6), have been synthesized. A mixture of MCl2·x H2O(M=Mn, Co) in MeOH(FeCl2·4H2O in MeCN) and the stoichiometric amount of Py2S2 was stirred for 4 h at room temperature, then these aiming products 1, 2 and 3 could be obtained by purification. A mixture of MPy2S2Cl2(M=Co, Ni) in MeOH and two equivalents of KSCN or NaN3 was stirred for 4 h at room temperature. After that, complexes 4, 5 and 6 could be got by purifying. For 1, 2, 3, 4 and 5, the metal centers are hexa-coordinated in a similar distorted octahedral geometry and the crystal structures have the same space group Pbcn. The crystal structure of compound 6 belongs to monoclinic with space group P21/c. The coordinated atoms around M(Ⅱ) are two pyridyl N atoms(N(1) and N(2)), two thioether S atoms(S(1) and S(2)) and two chloride ions(Cl(1) and Cl(2)) in compounds 1, 2, and 3, but in 4, 5, and 6, two chloride ions(Cl(1) and Cl(2)) are replaced by another two N atoms from N3- or NCS-.
Six first row transition metal complexes with 1,6-bis(2'-pyridyl)-2,5-dithiahexane(Py2S2), namely, MnPy2S2Cl2(1), FePy2S2Cl2(2), CoPy2S2Cl(3), CoPy2S2(SCN)2(4), NiPy2S2(SCN)2(5) and NiPy2S2(N3)2(6), have been synthesized. A mixture of MCl2·x H2O(M=Mn, Co) in MeOH(FeCl2·4H2O in MeCN) and the stoichiometric amount of Py2S2 was stirred for 4 h at room temperature, then these aiming products 1, 2 and 3 could be obtained by purification. A mixture of MPy2S2Cl2(M=Co, Ni) in MeOH and two equivalents of KSCN or NaN3 was stirred for 4 h at room temperature. After that, complexes 4, 5 and 6 could be got by purifying. For 1, 2, 3, 4 and 5, the metal centers are hexa-coordinated in a similar distorted octahedral geometry and the crystal structures have the same space group Pbcn. The crystal structure of compound 6 belongs to monoclinic with space group P21/c. The coordinated atoms around M(Ⅱ) are two pyridyl N atoms(N(1) and N(2)), two thioether S atoms(S(1) and S(2)) and two chloride ions(Cl(1) and Cl(2)) in compounds 1, 2, and 3, but in 4, 5, and 6, two chloride ions(Cl(1) and Cl(2)) are replaced by another two N atoms from N3- or NCS-.
2016, 35(9): 1461-1468
doi: 10.14102/j.cnki.0254-5861.2011-1187
Abstract:
A novel Zr-substituted polyoxometalate(POM) H2K3[Na6(H2O)9] [Zr3Na3O3(H2O)3-(GeW9O34)2]·12H2O(1) has been made under hydrothermal conditions. 1 was characterized by infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are:H50O95Na9K3Ge2Zr3W(1)8, hexagonal space group P63/mmc, a=15.2251(6), b=15.2251(6), c=25.035(2)Å, V=5025.7(6)Å3, Z=2, Dc=3.716 mg/m3, μ=21.648 mm-1, F(000)=4726, the final R=0.0259 and wR=0.0647 for 1487 observed reflections with I>2σ(I). Single-crystal X-ray structure analysis reveals that 1 exhibits a 3-dimensional framework structure based on Zr3Na3-substituted polyanions[Zr3Na3O3(H2O)3(GeW9O34)2]11- and [Na6(H2O)9]6+ clusters building blocks. UV-Vis spectrum indicates that 1 is a wide-gap semiconductor. In addition, the proton-conducting property of 1 was also investigated.
A novel Zr-substituted polyoxometalate(POM) H2K3[Na6(H2O)9] [Zr3Na3O3(H2O)3-(GeW9O34)2]·12H2O(1) has been made under hydrothermal conditions. 1 was characterized by infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are:H50O95Na9K3Ge2Zr3W(1)8, hexagonal space group P63/mmc, a=15.2251(6), b=15.2251(6), c=25.035(2)Å, V=5025.7(6)Å3, Z=2, Dc=3.716 mg/m3, μ=21.648 mm-1, F(000)=4726, the final R=0.0259 and wR=0.0647 for 1487 observed reflections with I>2σ(I). Single-crystal X-ray structure analysis reveals that 1 exhibits a 3-dimensional framework structure based on Zr3Na3-substituted polyanions[Zr3Na3O3(H2O)3(GeW9O34)2]11- and [Na6(H2O)9]6+ clusters building blocks. UV-Vis spectrum indicates that 1 is a wide-gap semiconductor. In addition, the proton-conducting property of 1 was also investigated.
2016, 35(9): 1469-1476
doi: 10.14102/j.cnki.0254-5861.2011-1183
Abstract:
The interaction of Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ) with dipyridine quinoxaline ligand 2,3-bis(2-pyridyl) quinoxaline(DPQ) were investigated, and three new complexes have been synthesized and characterized. Complex 1 exhibits a 0D dual-core structure, complex 2 is a 0D tetra nuclear case based on a dual-core Cu unit, and complex 3 shows a one-dimensional pipeline structure. Furthermore, the optical properties of complex and DPQ were also investigated, and the results showed that the fluorescence intensity of complexes was weaker than that of ligand DPQ.
The interaction of Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ) with dipyridine quinoxaline ligand 2,3-bis(2-pyridyl) quinoxaline(DPQ) were investigated, and three new complexes have been synthesized and characterized. Complex 1 exhibits a 0D dual-core structure, complex 2 is a 0D tetra nuclear case based on a dual-core Cu unit, and complex 3 shows a one-dimensional pipeline structure. Furthermore, the optical properties of complex and DPQ were also investigated, and the results showed that the fluorescence intensity of complexes was weaker than that of ligand DPQ.
