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2015 Volume 34 Issue 8
2015, 34(8): 1151-1160
doi: 10.14102/j.cnki.0254-5861.2011-0657
Abstract:
The reaction mechanism of CHF radical with HNCO was investigated by the B3LYP method of density functional theory (DFT), while the geometries and harmonic vibration frequencies of reactants, intermediates, transition states and products were calculated at the B3LYP/6-311++G** level. In the temperature range of 100~2600 K, the statistical thermody-namics and Eyring transition state theory with Winger correction were used to study the thermodynamic and kinetic characters of the channel with low energy barrier. In addition, the analysis on the combining interaction between CHF radical and HNCO was performed by atom-in-molecules theory (AIM) and natural bond orbitals (NBO) analysis. The calculation results indicated that the reaction of CHF radical with HNCO had ten channels, and the channel of NH direct extraction (CHF+HNCO→IM6→TS7→IM7→CHFNH+CO) in singlet state was the main channel with low potential energy and high equilibrium constant and reaction rate constant. CHFNH and CO were the main products.
The reaction mechanism of CHF radical with HNCO was investigated by the B3LYP method of density functional theory (DFT), while the geometries and harmonic vibration frequencies of reactants, intermediates, transition states and products were calculated at the B3LYP/6-311++G** level. In the temperature range of 100~2600 K, the statistical thermody-namics and Eyring transition state theory with Winger correction were used to study the thermodynamic and kinetic characters of the channel with low energy barrier. In addition, the analysis on the combining interaction between CHF radical and HNCO was performed by atom-in-molecules theory (AIM) and natural bond orbitals (NBO) analysis. The calculation results indicated that the reaction of CHF radical with HNCO had ten channels, and the channel of NH direct extraction (CHF+HNCO→IM6→TS7→IM7→CHFNH+CO) in singlet state was the main channel with low potential energy and high equilibrium constant and reaction rate constant. CHFNH and CO were the main products.
2015, 34(8): 1161-1169
doi: 10.14102/j.cnki.0254-5861.2011-0677
Abstract:
In the present work, the behavior of folic acid (FA) molecule adsorbed onto single-walled carbon nanotube (SWCNT) was examined using the DFT-B3LYP/6-31G* level. In order to obtain information about the binding features of SWCNT as adsorbent with FA molecule, several studies, including the structural and electronic parameters and also the Atoms in Molecules (AIM) analysis, were performed. It was observed that the FA molecule via hydrogen bond prefers to adsorb on SWCNT with adsorption energy of about -18.70 kcal/mol. The molecular orbitals (HOMO and LUMO), natural bond orbital (NBO) analysis, and density of states (DOS) plot indicated that a charge about 0.032|e|is transferred from the FA molecule to the nanotube. After solvation energy calculations, it was found that the presence of a polar solvent causes an increase in FA adsorption on the single-walled carbon nanotube. Topological features such as electron energy density (HC) and Laplacian of the electron density (▽2ρc) demonstrate partial covalent nature for H(116)…O(10) interaction in the FA/SWCNT complex. According to the calculated results, the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.
In the present work, the behavior of folic acid (FA) molecule adsorbed onto single-walled carbon nanotube (SWCNT) was examined using the DFT-B3LYP/6-31G* level. In order to obtain information about the binding features of SWCNT as adsorbent with FA molecule, several studies, including the structural and electronic parameters and also the Atoms in Molecules (AIM) analysis, were performed. It was observed that the FA molecule via hydrogen bond prefers to adsorb on SWCNT with adsorption energy of about -18.70 kcal/mol. The molecular orbitals (HOMO and LUMO), natural bond orbital (NBO) analysis, and density of states (DOS) plot indicated that a charge about 0.032|e|is transferred from the FA molecule to the nanotube. After solvation energy calculations, it was found that the presence of a polar solvent causes an increase in FA adsorption on the single-walled carbon nanotube. Topological features such as electron energy density (HC) and Laplacian of the electron density (▽2ρc) demonstrate partial covalent nature for H(116)…O(10) interaction in the FA/SWCNT complex. According to the calculated results, the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.
2015, 34(8): 1170-1178
doi: 10.14102/j.cnki.0254-5861.2011-0685
Abstract:
A new four-coordinated manganese compound Mn2(BPTC) (BPTC=biphenyl-2,4,4',6-tetracarboxylate) with flu topology net was synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis confirms its crystal belongs to the monoclinic system, space group C2/c with a=12.2092(11), b=14.6932(9), c=8.9998(10)Å, β=108.256(12)°, Z=4, V=1533.2(2)Å3, Dc=1.889 mg/m3, μ=1.69, F(000)=864, the final R=0.063 and wR=0.201 for 1407 observed reflections (I>2σ(I)). UV-Vis absorption spectrum shows the title compound has a strong absorption at 326 and 238 nm and the optical diffuse reflectance determination shows the band gap of the title compound is 3.15 eV. The theory calculation elucidated that the UV absorptions of the title compound mainly arise from the electron transition from bonding orbitals of BPTC4- ligand to the empty orbitals of BPTC4- and Mn(Ⅱ) ions.
A new four-coordinated manganese compound Mn2(BPTC) (BPTC=biphenyl-2,4,4',6-tetracarboxylate) with flu topology net was synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis confirms its crystal belongs to the monoclinic system, space group C2/c with a=12.2092(11), b=14.6932(9), c=8.9998(10)Å, β=108.256(12)°, Z=4, V=1533.2(2)Å3, Dc=1.889 mg/m3, μ=1.69, F(000)=864, the final R=0.063 and wR=0.201 for 1407 observed reflections (I>2σ(I)). UV-Vis absorption spectrum shows the title compound has a strong absorption at 326 and 238 nm and the optical diffuse reflectance determination shows the band gap of the title compound is 3.15 eV. The theory calculation elucidated that the UV absorptions of the title compound mainly arise from the electron transition from bonding orbitals of BPTC4- ligand to the empty orbitals of BPTC4- and Mn(Ⅱ) ions.
2015, 34(8): 1179-1186
doi: 10.14102/j.cnki.0254-5861.2011-0700
Abstract:
Dexmedetomidine and its novel salt have been synthesized and characterized by single-crystal XRD and TGA/DSG. Components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed. In this work, the salt strategy has been applied successfully to dexmedetomidine. One important parameter, i.e. stability, has also been significantly improved, which proves to be an important factor for solid dosage formulation. Furthermore, DSC/TGA analysis indicates that the salt maintains its crystallinity up to 300℃, suggesting a higher stability of the salt compared to pure dexmedetomidine.
Dexmedetomidine and its novel salt have been synthesized and characterized by single-crystal XRD and TGA/DSG. Components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed. In this work, the salt strategy has been applied successfully to dexmedetomidine. One important parameter, i.e. stability, has also been significantly improved, which proves to be an important factor for solid dosage formulation. Furthermore, DSC/TGA analysis indicates that the salt maintains its crystallinity up to 300℃, suggesting a higher stability of the salt compared to pure dexmedetomidine.
2015, 34(8): 1187-1196
doi: 10.14102/j.cnki.0254-5861.2011-0621
Abstract:
Konjac glucomannan (KGM) and sodium alginate were chosen as the research objects, and the hydrogen bond conformation of compound system was studied with the molecular dynamics simulation, which simulated the energy variety in composite process. Combining with Hamiltonian in quantum mechanics calculation, the mechanism of hydrogen bond in KGM and sodium alginate compound system stability was analyzed from a micro angle. The results showed that, the hydrogen bonds occurring between the molecule of KGM and sodium alginate are in large number, and they mainly appeared between the -OH on C(6), C(3) in the mannose residues of KGM and C(2), C(3) of sodium alginate. The formation of hydrogen bonds results in the energy expectation value of the Hamiltonian thermal density matrix of the compound system to be negative, the energy of the system to decrease, and the compounds tending to form stable conformations.
Konjac glucomannan (KGM) and sodium alginate were chosen as the research objects, and the hydrogen bond conformation of compound system was studied with the molecular dynamics simulation, which simulated the energy variety in composite process. Combining with Hamiltonian in quantum mechanics calculation, the mechanism of hydrogen bond in KGM and sodium alginate compound system stability was analyzed from a micro angle. The results showed that, the hydrogen bonds occurring between the molecule of KGM and sodium alginate are in large number, and they mainly appeared between the -OH on C(6), C(3) in the mannose residues of KGM and C(2), C(3) of sodium alginate. The formation of hydrogen bonds results in the energy expectation value of the Hamiltonian thermal density matrix of the compound system to be negative, the energy of the system to decrease, and the compounds tending to form stable conformations.
2015, 34(8): 1197-1202
doi: 10.14102/j.cnki.0254-5861.2011-0646
Abstract:
A novel crystal [(CH3O)2CO]3Li2[C2BF2O4]2 was synthesized and fully characterized by FT-IR and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system, P21/c space group, with a=8.1749(2), b=10.7449(2), c=12.8665(3)Å, β=94.654(2)°, V=1126.45(4)Å3, Z=2, Dc=1.644 g/cm, F(000)=568, μ=1.498 mm-1, Mr=557.77 g/mol, the final R=0.0334 and wR=0.0903. The structure analysis revealed that each Li atom is three-coordinated and adopts 1.5 O atoms of two different dimethyl carbonates and one O atom of C2BF2O4-. Thermal stability and infrared spectra analysis were studied and discussed.
A novel crystal [(CH3O)2CO]3Li2[C2BF2O4]2 was synthesized and fully characterized by FT-IR and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system, P21/c space group, with a=8.1749(2), b=10.7449(2), c=12.8665(3)Å, β=94.654(2)°, V=1126.45(4)Å3, Z=2, Dc=1.644 g/cm, F(000)=568, μ=1.498 mm-1, Mr=557.77 g/mol, the final R=0.0334 and wR=0.0903. The structure analysis revealed that each Li atom is three-coordinated and adopts 1.5 O atoms of two different dimethyl carbonates and one O atom of C2BF2O4-. Thermal stability and infrared spectra analysis were studied and discussed.
2015, 34(8): 1203-1216
doi: 10.14102/j.cnki.0254-5861.2011-0669
Abstract:
Owing to the merits of high catalytic activity, Pd-supported materials have received extensive attention. However, those materials always require complex and high-cost synthetic processes such as high-temperature calcination or H2 reduction, which seriously hinder their wide applications. In this work, a novel Pd reduction method was developed for Pd-supported TiO2 catalysts, in which the Pd2+ ions were partly reduced and homogeneously loaded on the surface of 8 nm TiO2 with the assistance of pre-produced surface Ti3+ ions. This facile preparation is calcination-free and cost-low. The excellent catalysts can produce H2 33 mmol/g/h under UV-vis light irradiation, and degrade nearly 10% methyl orange in 1 h visible-light irradiation, which is much higher than that of unloaded TiO2 or Pd/TiO2 prepared by traditional high-temperature calcination methods. Moreover, the resulting Pd-supported TiO2 nano-catalysts are also effective for colorless phenol degradation under visible-light. The reasons for these superior activities can be assigned to the co-existence of Pd0 and Pd2+ on the surface of TiO2 nanoparticles, which is closely related to the calcination-free synthetic process. UV-Vis absorbance spectra show that the obtained 0.53Pd/TiO2 is visible-light-driven and nitrogen physisorption isotherms indicate a high specific surface area of 203 m2/g. The preparation method reported herein may provide hints for obtaining other high photocatalytic activity Pd-based supported catalysts for hydrogen generation and methylene orange degradation.
Owing to the merits of high catalytic activity, Pd-supported materials have received extensive attention. However, those materials always require complex and high-cost synthetic processes such as high-temperature calcination or H2 reduction, which seriously hinder their wide applications. In this work, a novel Pd reduction method was developed for Pd-supported TiO2 catalysts, in which the Pd2+ ions were partly reduced and homogeneously loaded on the surface of 8 nm TiO2 with the assistance of pre-produced surface Ti3+ ions. This facile preparation is calcination-free and cost-low. The excellent catalysts can produce H2 33 mmol/g/h under UV-vis light irradiation, and degrade nearly 10% methyl orange in 1 h visible-light irradiation, which is much higher than that of unloaded TiO2 or Pd/TiO2 prepared by traditional high-temperature calcination methods. Moreover, the resulting Pd-supported TiO2 nano-catalysts are also effective for colorless phenol degradation under visible-light. The reasons for these superior activities can be assigned to the co-existence of Pd0 and Pd2+ on the surface of TiO2 nanoparticles, which is closely related to the calcination-free synthetic process. UV-Vis absorbance spectra show that the obtained 0.53Pd/TiO2 is visible-light-driven and nitrogen physisorption isotherms indicate a high specific surface area of 203 m2/g. The preparation method reported herein may provide hints for obtaining other high photocatalytic activity Pd-based supported catalysts for hydrogen generation and methylene orange degradation.
2015, 34(8): 1217-1223
doi: 10.14102/j.cnki.0254-5861.2011-0719
Abstract:
Thermoelectric (TE) materials can convert directly low-grade heat energy to electricity, and vice versa, which is highly expected to play an important role in the future energy management. The application practice demands efficient TE materials made of non-toxic and inexpensive components. Herein, we report a Ni substituted polycrystalline n-type bulk material In4-xNixSe3 (x=0~0.1). Based on density functional theory calculation, Ni tends to substitute at the In3 site in the In4Se3, which causes a monotonous unit cell volume reduction. At x=0.01, Ni substitution results in a sharp decrease in the carrier concentration (ne) in comparison with that of pure In4Se3, and then ne increases with the increase of Ni concentration. Ni substitution leads to a performance enhancement from 0.6 for pure In4Se3 to an optimum ZT value of 0.8 at 450℃.
Thermoelectric (TE) materials can convert directly low-grade heat energy to electricity, and vice versa, which is highly expected to play an important role in the future energy management. The application practice demands efficient TE materials made of non-toxic and inexpensive components. Herein, we report a Ni substituted polycrystalline n-type bulk material In4-xNixSe3 (x=0~0.1). Based on density functional theory calculation, Ni tends to substitute at the In3 site in the In4Se3, which causes a monotonous unit cell volume reduction. At x=0.01, Ni substitution results in a sharp decrease in the carrier concentration (ne) in comparison with that of pure In4Se3, and then ne increases with the increase of Ni concentration. Ni substitution leads to a performance enhancement from 0.6 for pure In4Se3 to an optimum ZT value of 0.8 at 450℃.
2015, 34(8): 1224-1230
doi: 10.14102/j.cnki.0254-5861.2011-0802
Abstract:
Two enantiomeric 2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d] pyrimidin-4-amine derivatives were synthesized by nucleophilic substitution of two chiral amines with 4-chloro-2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidine, which started from 2-amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile, trifluoroacetic acid (TFA) and phosphoryl trichloride via one-pot procedure. Their structures were determined by single-crystal X-ray diffraction. Enantiomer (R)-3,(R)-N-(1-phenylethyl)-2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidin-4-amine crystallizes in the tetragonal system, space group P43 with a=8.6847(6), b=8.6847(6), c=22.419(2)Å, V=1690.9(3)Å3, Z=4, Dc=1.428 g/cm3, μ=0.228 mm-1, F(000)=752, the final R=0.0463 and wR=0.1257 for 3442 observed reflections with I>2σ(I). Enantiomer (S)-3,(S)-N-(1-phenylethyl)-2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidin-4-amine crystallizes in the tetragonal system, space group P41 with a=8.688, b=8.688, c=22.421Å, V=1692.4Å3, Z=4, Dc=1.426 g/cm3, μ=0.227 mm-1, F(000)=752, the final R=0.0682 and wR=0.1806 for 3182 observed reflections with I>2σ(I). The preliminary bioassay indicated that the R-enantiomer exhibits higher antitumor activity against MCF-7 than gefitinib.
Two enantiomeric 2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d] pyrimidin-4-amine derivatives were synthesized by nucleophilic substitution of two chiral amines with 4-chloro-2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidine, which started from 2-amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile, trifluoroacetic acid (TFA) and phosphoryl trichloride via one-pot procedure. Their structures were determined by single-crystal X-ray diffraction. Enantiomer (R)-3,(R)-N-(1-phenylethyl)-2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidin-4-amine crystallizes in the tetragonal system, space group P43 with a=8.6847(6), b=8.6847(6), c=22.419(2)Å, V=1690.9(3)Å3, Z=4, Dc=1.428 g/cm3, μ=0.228 mm-1, F(000)=752, the final R=0.0463 and wR=0.1257 for 3442 observed reflections with I>2σ(I). Enantiomer (S)-3,(S)-N-(1-phenylethyl)-2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidin-4-amine crystallizes in the tetragonal system, space group P41 with a=8.688, b=8.688, c=22.421Å, V=1692.4Å3, Z=4, Dc=1.426 g/cm3, μ=0.227 mm-1, F(000)=752, the final R=0.0682 and wR=0.1806 for 3182 observed reflections with I>2σ(I). The preliminary bioassay indicated that the R-enantiomer exhibits higher antitumor activity against MCF-7 than gefitinib.
2015, 34(8): 1231-1237
doi: 10.14102/j.cnki.0254-5861.2011-0717
Abstract:
Compounds 1 (C15H17ClF3N3O3, Mr=379) and 2 (C14H14ClF3N4OS, Mr=378) have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system, space group P1 with a=6.0223(19), b=9.324(3), c=15.936(5)Å, α=80.687(5), β=87.289(5), γ=86.097(5)°, V=880.4(5)Å3, Z=2, Dc=1.433 g/cm3, μ(MoKα)=0.266 mm-1, F(000)=392, R=0.0861 and wR=0.1999 for 2022 observed reflections with I>2σ(I). Crystal 2 belongs to the triclinic system, space group P1 with a=7.7029(15), b=8.3371(16), c=14.410(3)Å, α=100.672(3), β=103.168(3), γ=98.726(3)°, V=876.1(3)Å3, Z=2, Dc=1.451 g/cm3, μ(MoKα)=0.379 mm-1, F(000)=388, R=0.0672 and wR=0.2105 for 2725 observed reflections with I>2σ(I). Although the two compounds are similar with the same pyrazole and pyrethroid units, X-ray analysis reveals that their structures are completely different.
Compounds 1 (C15H17ClF3N3O3, Mr=379) and 2 (C14H14ClF3N4OS, Mr=378) have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system, space group P1 with a=6.0223(19), b=9.324(3), c=15.936(5)Å, α=80.687(5), β=87.289(5), γ=86.097(5)°, V=880.4(5)Å3, Z=2, Dc=1.433 g/cm3, μ(MoKα)=0.266 mm-1, F(000)=392, R=0.0861 and wR=0.1999 for 2022 observed reflections with I>2σ(I). Crystal 2 belongs to the triclinic system, space group P1 with a=7.7029(15), b=8.3371(16), c=14.410(3)Å, α=100.672(3), β=103.168(3), γ=98.726(3)°, V=876.1(3)Å3, Z=2, Dc=1.451 g/cm3, μ(MoKα)=0.379 mm-1, F(000)=388, R=0.0672 and wR=0.2105 for 2725 observed reflections with I>2σ(I). Although the two compounds are similar with the same pyrazole and pyrethroid units, X-ray analysis reveals that their structures are completely different.
2015, 34(8): 1238-1246
doi: 10.14102/j.cnki.0254-5861.2011-0642
Abstract:
Two new complexes [Pd(L-phe)2·2H2O] (1) and [Pd(4,4'-dcbpy)(en)·H2O] (2) (L-phe=L-phenylalanine, 4,4'-dcbpy=2,2'-bipyridyl-4,4'-dicarboxylate, en=ethylenediamine) were synthesized and characterized. L-phenylalanine was in situ formed via the hydrolysis of N-(tert-butoxycarbonyl)-L-phenylalanine, and ethylenediamine came from the in situ reaction of piperazine (pip) under hydrothermal conditions. The single-crystal X-ray structure analyses reveal that the Pd(Ⅱ) ion constructs a square planer coordination geometry in complexes 1 and 2, respectively. Complex 1 extends into a 2D layered structure via H-bond interactions and complex 2 connects into a 3D network through hydrogen bonds and π-π stacking interactions. The interactions of 1 and 2 with fish sperm DNA (FS-DNA) were examined via UV-Vis absorption spectra and fluorescence spectroscopy. The cleavage reaction for plasmid DNA has been assayed by agarose gel electrophoresis. The results indicate that two complexes interact with DNA and the insertion is the main binding mode.
Two new complexes [Pd(L-phe)2·2H2O] (1) and [Pd(4,4'-dcbpy)(en)·H2O] (2) (L-phe=L-phenylalanine, 4,4'-dcbpy=2,2'-bipyridyl-4,4'-dicarboxylate, en=ethylenediamine) were synthesized and characterized. L-phenylalanine was in situ formed via the hydrolysis of N-(tert-butoxycarbonyl)-L-phenylalanine, and ethylenediamine came from the in situ reaction of piperazine (pip) under hydrothermal conditions. The single-crystal X-ray structure analyses reveal that the Pd(Ⅱ) ion constructs a square planer coordination geometry in complexes 1 and 2, respectively. Complex 1 extends into a 2D layered structure via H-bond interactions and complex 2 connects into a 3D network through hydrogen bonds and π-π stacking interactions. The interactions of 1 and 2 with fish sperm DNA (FS-DNA) were examined via UV-Vis absorption spectra and fluorescence spectroscopy. The cleavage reaction for plasmid DNA has been assayed by agarose gel electrophoresis. The results indicate that two complexes interact with DNA and the insertion is the main binding mode.
2015, 34(8): 1247-1252
doi: 10.14102/j.cnki.0254-5861.2011-0652
Abstract:
A new organic-inorganic hybrid copper-substituted arsenatotungstate complex formulated as [{Cu(phen)(en)}{Cu(phen)}{Cu3(phen)3(α-AsW9O33)}](OH)·3H2O (1, en=ethylene-diamine, 1,10-phen=1,10-phenanthroline) has been synthesized by controlling the reaction process and characterized by infrared (IR) spectroscopy, elemental analysis, and thermogravimetric (TG) analysis. Crystal data for 1: C62H56AsCu5N12O37W9, Mr=3608.46, monoclinic, space group P21/c, a=13.245(4), b=25.692(9), c=24.670(8)Å, β=99.251(6)°, V=8286(5)Å3, Z=4, GOOF=1.103, R=0.0560, wR=0.1285. In 1, the vacant sites of the trivacant Keggin anion [α-AsW9O33]9- are occupied by three same copper coordination cations [Cu(phen)]2+. Meanwhile, the lacunary anion [α-AsW9O33]9- is capped by two kinds of copper coordination cations [Cu(phen)]2+ and [Cu(phen)(en)]2+, resulting in an unprecedented polycation structure with Cs symmetry.
A new organic-inorganic hybrid copper-substituted arsenatotungstate complex formulated as [{Cu(phen)(en)}{Cu(phen)}{Cu3(phen)3(α-AsW9O33)}](OH)·3H2O (1, en=ethylene-diamine, 1,10-phen=1,10-phenanthroline) has been synthesized by controlling the reaction process and characterized by infrared (IR) spectroscopy, elemental analysis, and thermogravimetric (TG) analysis. Crystal data for 1: C62H56AsCu5N12O37W9, Mr=3608.46, monoclinic, space group P21/c, a=13.245(4), b=25.692(9), c=24.670(8)Å, β=99.251(6)°, V=8286(5)Å3, Z=4, GOOF=1.103, R=0.0560, wR=0.1285. In 1, the vacant sites of the trivacant Keggin anion [α-AsW9O33]9- are occupied by three same copper coordination cations [Cu(phen)]2+. Meanwhile, the lacunary anion [α-AsW9O33]9- is capped by two kinds of copper coordination cations [Cu(phen)]2+ and [Cu(phen)(en)]2+, resulting in an unprecedented polycation structure with Cs symmetry.
2015, 34(8): 1253-1258
doi: 10.14102/j.cnki.0254-5861.2011-0663
Abstract:
The endohedral plumbaspherene cluster anion [Rh@Pb12]3- was synthesized by the reaction of K4Pb9 with Rh(PPh3)3Cl in ethylenediamine (en) solution in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), and characterized by single-crystal X-ray diffraction and energy-dispersive X-ray (EDX) analysis. The novel zintl ion cluster [Rh@Pb12]3- represents the first structurally characterized plumbaspherene Pb12 cluster with Ih point symmetry encapsulating a group 9 element in a spherical tetrel deltahedron. And the discovery of anion [Rh@Pb12]3- also provides direct proof for previous reports on the observation of [M@Pb12]x± (clusters in mass spectrometric experiments proved by quantum-chemical calculations). DFT computations indicate that the icosahedral cluster anion [Rh@Pb12]3- is isostructural and isoelectronic with [Ir@Sn12]3-.
The endohedral plumbaspherene cluster anion [Rh@Pb12]3- was synthesized by the reaction of K4Pb9 with Rh(PPh3)3Cl in ethylenediamine (en) solution in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), and characterized by single-crystal X-ray diffraction and energy-dispersive X-ray (EDX) analysis. The novel zintl ion cluster [Rh@Pb12]3- represents the first structurally characterized plumbaspherene Pb12 cluster with Ih point symmetry encapsulating a group 9 element in a spherical tetrel deltahedron. And the discovery of anion [Rh@Pb12]3- also provides direct proof for previous reports on the observation of [M@Pb12]x± (clusters in mass spectrometric experiments proved by quantum-chemical calculations). DFT computations indicate that the icosahedral cluster anion [Rh@Pb12]3- is isostructural and isoelectronic with [Ir@Sn12]3-.
2015, 34(8): 1259-1264
doi: 10.14102/j.cnki.0254-5861.2011-0612
Abstract:
A new Ag(Ⅰ) coordination polymer, {[Ag(1,3-BIP)(H2O)][Ag(1,3-BIP)(PMA)0.5·4H2O}n (PMA=1,2,4,5-benzenetricarboxylic acid, 1,3-BIP=1,3-bis(imidazole)propane), have been synthesized and characterized by single-crystal X-ray diffraction, powder XR1D, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that the title complex is formed by 1D polymeric cationic chains of [Ag(1,3-BIP)(H2O)]nn+ and 2D polymetric anionic layer of [Ag(1,3-BIP)(PMA)0.5]nn-, which are further linked by intermolecular H-bonding to form a 3D supramolecular framework. In addition, the photoluminescence property of the title complex in the solid state at room temperature was also investigated.
A new Ag(Ⅰ) coordination polymer, {[Ag(1,3-BIP)(H2O)][Ag(1,3-BIP)(PMA)0.5·4H2O}n (PMA=1,2,4,5-benzenetricarboxylic acid, 1,3-BIP=1,3-bis(imidazole)propane), have been synthesized and characterized by single-crystal X-ray diffraction, powder XR1D, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that the title complex is formed by 1D polymeric cationic chains of [Ag(1,3-BIP)(H2O)]nn+ and 2D polymetric anionic layer of [Ag(1,3-BIP)(PMA)0.5]nn-, which are further linked by intermolecular H-bonding to form a 3D supramolecular framework. In addition, the photoluminescence property of the title complex in the solid state at room temperature was also investigated.
2015, 34(8): 1265-1272
doi: 10.14102/j.cnki.0254-5861.2011-0650
Abstract:
Two new europium-based metal-organic-frameworks (MOFs), namely [NMe4][Eu(m-BDC)2] (1) and [Eu3(p-BDC)4(ClO4)(H2O)4] (2), have been synthesized and structurally characte-rized. Single-crystal X-ray diffraction studies reveal that 1 crystallizes in the monoclinic system, space group P21/c with a 2D layer structure, while 2 crystallizes in the orthorhombic system, space group Pccn with a 3D net structure. Both 1 and 2 have strong characteristic Eu(Ⅲ) emissions at visible red region and the quantum yields can reach up to 78.1 and 46.0%, respectively. The high luminescent efficiency may be attributed to the efficient energy transition from the ligands to the Eu(Ⅲ) center.
Two new europium-based metal-organic-frameworks (MOFs), namely [NMe4][Eu(m-BDC)2] (1) and [Eu3(p-BDC)4(ClO4)(H2O)4] (2), have been synthesized and structurally characte-rized. Single-crystal X-ray diffraction studies reveal that 1 crystallizes in the monoclinic system, space group P21/c with a 2D layer structure, while 2 crystallizes in the orthorhombic system, space group Pccn with a 3D net structure. Both 1 and 2 have strong characteristic Eu(Ⅲ) emissions at visible red region and the quantum yields can reach up to 78.1 and 46.0%, respectively. The high luminescent efficiency may be attributed to the efficient energy transition from the ligands to the Eu(Ⅲ) center.
2015, 34(8): 1273-1280
doi: 10.14102/j.cnki.0254-5861.2011-0683
Abstract:
Eight new ZnⅡ-YⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes: MZnL2(NO3)3 (M=Y (1), La (2), Pr (3), Nd (4), Eu (5), Gd (6), Dy (7), Er (8); L=2-(((2-(imidazo[1,5-a]pyridin-3-yl)phenyl)imino)methyl)-6-methoxyphenol), have been rationally synthesized under solvothermal conditions and characterized by IR, elemental analyses (EA), single-crystal X-ray diffraction, and powder XRD. Furthermore, luminescence in the visible region for solids 1~8 suggested zinc/ligand-centered emission at room temperature.
Eight new ZnⅡ-YⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes: MZnL2(NO3)3 (M=Y (1), La (2), Pr (3), Nd (4), Eu (5), Gd (6), Dy (7), Er (8); L=2-(((2-(imidazo[1,5-a]pyridin-3-yl)phenyl)imino)methyl)-6-methoxyphenol), have been rationally synthesized under solvothermal conditions and characterized by IR, elemental analyses (EA), single-crystal X-ray diffraction, and powder XRD. Furthermore, luminescence in the visible region for solids 1~8 suggested zinc/ligand-centered emission at room temperature.
2015, 34(8): 1281-1287
doi: 10.14102/j.cnki.0254-5861.2011-0653
Abstract:
One cobalt coordinated polymer with 2-fold parallel interpenetration 3D architecture based on flexible 5-(imidazol-1-ylmethyl)isophthalate (L2-) as a main ligand and 4,4'-bipyridine (bpy) as a nitrogen-containing ancillary ligand, {[CoL(bpy)0.5(H2O)3]2}n (1), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction (PXRD), IR spectra, Uv/vis spectra, thermal gravimetric analyses (TGA) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a=26.323(4), b=14.696(2), c=26.630(4)Å, β=157.747(4)°, V=3901.2(1)Å3, Z=8, Mr=435.27, Dc=1.480 g/cm3, μ=0.923 mm-1, Rint=0.0900, F(000)=1792, the final R=0.0722 and wR=0.0946 for 3641 observed reflections (I>2σ(I)). Complex 1 exhibits a two-fold interpenetration 3D framework. As a single net of the 2-fold interpenetration structure, the L2- anion of complex 1, as a bridging ligand, connects the Co(Ⅱ) ion to form two-dimensional layers (Co3L3)n which are further linked to build a three-dimensional framework by bpy ligand.
One cobalt coordinated polymer with 2-fold parallel interpenetration 3D architecture based on flexible 5-(imidazol-1-ylmethyl)isophthalate (L2-) as a main ligand and 4,4'-bipyridine (bpy) as a nitrogen-containing ancillary ligand, {[CoL(bpy)0.5(H2O)3]2}n (1), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction (PXRD), IR spectra, Uv/vis spectra, thermal gravimetric analyses (TGA) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a=26.323(4), b=14.696(2), c=26.630(4)Å, β=157.747(4)°, V=3901.2(1)Å3, Z=8, Mr=435.27, Dc=1.480 g/cm3, μ=0.923 mm-1, Rint=0.0900, F(000)=1792, the final R=0.0722 and wR=0.0946 for 3641 observed reflections (I>2σ(I)). Complex 1 exhibits a two-fold interpenetration 3D framework. As a single net of the 2-fold interpenetration structure, the L2- anion of complex 1, as a bridging ligand, connects the Co(Ⅱ) ion to form two-dimensional layers (Co3L3)n which are further linked to build a three-dimensional framework by bpy ligand.
2015, 34(8): 1288-1294
doi: 10.14102/j.cnki.0254-5861.2011-0691
Abstract:
A novel two-dimensional metal organic coordination compound based on flexible 1,3,5-tri(4-carboxyphenoxy)benzene (H3TCPB), {[Mg1.5(TCPB)(DMF)(H2O)]·(DMF)}n (1), has been prepared and structurally characterized by single-crystal X-ray diffraction, TGA, and PXRD measurements. Complex 1 crystalizes in triclinic, space group P1 with a=10.2521(6), b=11.0974(7), c=16.1113(9)Å, C33H31Mg1.5N2O12, Mr=684.06, V=1669.46(17)Å3, Z=2, Dc=1.361 g·cm-3, μ=0.129 mm-1, F(000)=714, 3.06≤θ≤25°, λMoKα)=0.71073Å, T=273(2) K, the final R=0.0386, wR=0.0892 and S=1.031. X-ray diffraction analysis reveals that complex 1 possesses a two-dimensional framework constructed by trinuclear Mg SBUs and three-connected TCPB3- linker. In addition, the solid state luminescent property of complex 1 was also investigated at room temperature.
A novel two-dimensional metal organic coordination compound based on flexible 1,3,5-tri(4-carboxyphenoxy)benzene (H3TCPB), {[Mg1.5(TCPB)(DMF)(H2O)]·(DMF)}n (1), has been prepared and structurally characterized by single-crystal X-ray diffraction, TGA, and PXRD measurements. Complex 1 crystalizes in triclinic, space group P1 with a=10.2521(6), b=11.0974(7), c=16.1113(9)Å, C33H31Mg1.5N2O12, Mr=684.06, V=1669.46(17)Å3, Z=2, Dc=1.361 g·cm-3, μ=0.129 mm-1, F(000)=714, 3.06≤θ≤25°, λMoKα)=0.71073Å, T=273(2) K, the final R=0.0386, wR=0.0892 and S=1.031. X-ray diffraction analysis reveals that complex 1 possesses a two-dimensional framework constructed by trinuclear Mg SBUs and three-connected TCPB3- linker. In addition, the solid state luminescent property of complex 1 was also investigated at room temperature.
2015, 34(8): 1295-1299
doi: 10.14102/j.cnki.0254-5861.2011-0692
Abstract:
In this work, we report a new two-dimensional Sr(Ⅱ) coordination polymer, namely, [Sr(L)(phen)(H2O)] (1), based on 3,5-dinitro-salicylic acid (H2L) and 1,10-phenanthroline (phen). It crystallizes in monoclinic, space group P21/c with a=15.479(3), b=9.4020(19), c=13.884(3)Å, β=103.76(3)°, V=1962.5(7)Å3, Z=4, C19H12SrN4O8, Mr=511.95, Dc=1.733 g/cm3, F(000)=1024, μ(MoKa)=2.805 mm-1, R=0.0411 and wR=0.1069. In 1, each L anion bridges three Sr(Ⅱ) atoms by using carboxylate and hydroxyl groups, yielding a two-dimensional layer structure. The phen ligands are alternately attached to both sides of the layer. The π-π stacking between L and phen in the same layer and hydrogen-bonding interactions between water molecule and carboxylate oxygen atom play an important role in stabilizing the layer structure of 1. The solid state luminescent property of 1 was also studied at room temperature.
In this work, we report a new two-dimensional Sr(Ⅱ) coordination polymer, namely, [Sr(L)(phen)(H2O)] (1), based on 3,5-dinitro-salicylic acid (H2L) and 1,10-phenanthroline (phen). It crystallizes in monoclinic, space group P21/c with a=15.479(3), b=9.4020(19), c=13.884(3)Å, β=103.76(3)°, V=1962.5(7)Å3, Z=4, C19H12SrN4O8, Mr=511.95, Dc=1.733 g/cm3, F(000)=1024, μ(MoKa)=2.805 mm-1, R=0.0411 and wR=0.1069. In 1, each L anion bridges three Sr(Ⅱ) atoms by using carboxylate and hydroxyl groups, yielding a two-dimensional layer structure. The phen ligands are alternately attached to both sides of the layer. The π-π stacking between L and phen in the same layer and hydrogen-bonding interactions between water molecule and carboxylate oxygen atom play an important role in stabilizing the layer structure of 1. The solid state luminescent property of 1 was also studied at room temperature.
