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2020 Volume 39 Issue 9
2020, 39(9): 1559-1563
doi: 10.14102/j.cnki.0254-5861.2011-2959
Abstract:
Design and exploratory synthesis of novel infrared nonlinear optical chalcogenides have drawn extensive concerns owing to their excellent overall performance and important role in laser industry. During the past decades, a large number of infrared nonlinear optical chalcogenides have been developed and many effective design strategies have been summarized, which illuminates the path of future explorations. In this perspective, we discuss the feasibility and effectiveness of the representative design ideas. Moreover, we point out some topics to be investigated and discuss the future research directions.
Design and exploratory synthesis of novel infrared nonlinear optical chalcogenides have drawn extensive concerns owing to their excellent overall performance and important role in laser industry. During the past decades, a large number of infrared nonlinear optical chalcogenides have been developed and many effective design strategies have been summarized, which illuminates the path of future explorations. In this perspective, we discuss the feasibility and effectiveness of the representative design ideas. Moreover, we point out some topics to be investigated and discuss the future research directions.
2020, 39(9): 1564-1570
doi: 10.14102/j.cnki.0254-5861.2011-2962
Abstract:
The second-order nonlinear optical (NLO) materials play an important role in the application and development of laser techniques. For various candidates, those in the middle infrared (MIR) region are far from the market's requirement. Therefore, it is necessary to explore new ones with better performance. For their exploration, the inclusion of multiple anions in one structure has been proved to be a successful strategy. The NLO property contains several aspects, and different anions may contribute to different aspects. Therefore, the multiple anions' combination may give an opportunity to obtain NLO materials with desirable properties. Here, we make a short but clear summary on the MIR NLO-active chalcogenides and halides containing multiple anions, as most of them exhibit nice NLO performances.
The second-order nonlinear optical (NLO) materials play an important role in the application and development of laser techniques. For various candidates, those in the middle infrared (MIR) region are far from the market's requirement. Therefore, it is necessary to explore new ones with better performance. For their exploration, the inclusion of multiple anions in one structure has been proved to be a successful strategy. The NLO property contains several aspects, and different anions may contribute to different aspects. Therefore, the multiple anions' combination may give an opportunity to obtain NLO materials with desirable properties. Here, we make a short but clear summary on the MIR NLO-active chalcogenides and halides containing multiple anions, as most of them exhibit nice NLO performances.
2020, 39(9): 1571-1577
doi: 10.14102/j.cnki.0254-5861.2011-2968
Abstract:
Ultraviolet (UV) nonlinear optical (NLO) crystal materials are hailed as the "chip" of the optoelectronic industry for they play a unique and crucial role in many newly developed scientific and technological applications. At present, due to the relatively single frequency doubling gene types of traditional NLO materials, the service performance of UV NLO materials is fundamentally restricted. Therefore, there is an urgent need to develop new synthesis methods, search for novel functional groups, expand new UV NLO materials systems, screen new high-performance crystals, and then break through performance bottlenecks. Herein, we review the recent progresses on UV NLO crystal materials. Furthermore, we prospect that these recently developed approaches will continuously extend their advantages in developing superior UV NLO materials in the near future.
Ultraviolet (UV) nonlinear optical (NLO) crystal materials are hailed as the "chip" of the optoelectronic industry for they play a unique and crucial role in many newly developed scientific and technological applications. At present, due to the relatively single frequency doubling gene types of traditional NLO materials, the service performance of UV NLO materials is fundamentally restricted. Therefore, there is an urgent need to develop new synthesis methods, search for novel functional groups, expand new UV NLO materials systems, screen new high-performance crystals, and then break through performance bottlenecks. Herein, we review the recent progresses on UV NLO crystal materials. Furthermore, we prospect that these recently developed approaches will continuously extend their advantages in developing superior UV NLO materials in the near future.
2020, 39(9): 1578-1584
doi: 10.14102/j.cnki.0254-5861.2011-2965
Abstract:
A new double alkali metal borate, LiRbB8O13, has been obtained in the sealed system. Its structure consists of two kinds of independent interpenetrating 3D frameworks composed of the fundamental building block, [B8O16]8–. It crystallizes in the P21/c space group with a = 10.950(6), b = 7.689(4), c = 11.375(7) Å, β = 96.653(7)°, V = 951.2(9) Å3, Z = 4, F(000) = 736, Dc = 2.702 g/cm3, Mr = 386.89 and μ = 5.289 mm–1. The final R = 0.0547 and wR = 0.1224. The UV-Vis-NIR diffuse reflectance spectrum, infrared spectrum and the first-principle theoretical studies show that the title compound possesses a short cut-off edge and large birefringence.
A new double alkali metal borate, LiRbB8O13, has been obtained in the sealed system. Its structure consists of two kinds of independent interpenetrating 3D frameworks composed of the fundamental building block, [B8O16]8–. It crystallizes in the P21/c space group with a = 10.950(6), b = 7.689(4), c = 11.375(7) Å, β = 96.653(7)°, V = 951.2(9) Å3, Z = 4, F(000) = 736, Dc = 2.702 g/cm3, Mr = 386.89 and μ = 5.289 mm–1. The final R = 0.0547 and wR = 0.1224. The UV-Vis-NIR diffuse reflectance spectrum, infrared spectrum and the first-principle theoretical studies show that the title compound possesses a short cut-off edge and large birefringence.
2020, 39(9): 1585-1593
doi: 10.14102/j.cnki.0254-5861.2011-2663
Abstract:
Mineral medicine, especially those containing heavy metals, is one of the characteristics of traditional Chinese medicine. A famous mineral medicine, realgar, containing heavy metal arsenic with a chemical formula of As4S4, has the function of detoxification, killing bacteria and viruses, and eliminating dampness and phlegm. Different As4S4 isomers are likely to have different drug effects and pharmacological actions. Therefore, it is of great scientific significance to find more stable As4S4 isomers. In view of this, ab initio molecular orbital theory and density functional theory (DFT) have been used to study ten isomers of As4S4 at the B3LYP/6-31G*, B3LYP/6-311+G*, B3LYP/6-311+G(3df, 2p) and MP2/(6-311+G*, LanL2MB) levels of theory. In addition to the two isomers having been studied previously, eight new isomers were investigated in the present paper. All the ten As4S4 isomers were proved to be true local minima on their potential energy surfaces. The calculated NICS values and molecular orbital analyses showed that, the D2d symmetric As4S4, isomer 1, may be σ-aromatic. The study proves that ten As4S4 isomers are stable thermodynamically, and are highly desirable for the future theoretical study of realgar.
Mineral medicine, especially those containing heavy metals, is one of the characteristics of traditional Chinese medicine. A famous mineral medicine, realgar, containing heavy metal arsenic with a chemical formula of As4S4, has the function of detoxification, killing bacteria and viruses, and eliminating dampness and phlegm. Different As4S4 isomers are likely to have different drug effects and pharmacological actions. Therefore, it is of great scientific significance to find more stable As4S4 isomers. In view of this, ab initio molecular orbital theory and density functional theory (DFT) have been used to study ten isomers of As4S4 at the B3LYP/6-31G*, B3LYP/6-311+G*, B3LYP/6-311+G(3df, 2p) and MP2/(6-311+G*, LanL2MB) levels of theory. In addition to the two isomers having been studied previously, eight new isomers were investigated in the present paper. All the ten As4S4 isomers were proved to be true local minima on their potential energy surfaces. The calculated NICS values and molecular orbital analyses showed that, the D2d symmetric As4S4, isomer 1, may be σ-aromatic. The study proves that ten As4S4 isomers are stable thermodynamically, and are highly desirable for the future theoretical study of realgar.
2020, 39(9): 1594-1600
doi: 10.14102/j.cnki.0254-5861.2011-2641
Abstract:
The structure of penicillin sulfoxide is rearranged to cephalosporins by the Morin rearrangement. It is a unit reaction for the preparation of various types of cephalosporins. In order to make better use of the reaction and in view of the shortage of the reaction theory, this study used m062x/6-311++G (d, p) to explore the possible ring-opening reaction of the penicillin sulfoxide. It is found that the isomer of (S)-sulfoxide is a necessary structure. At the same time, the intramolecular hydrogen bonding effect between the side-chain amide proton (-CONH-) and the sulfinyl oxygen (-SO) is the decisive structure factor for the formation of alkenyl in ring-opening reaction, and the best reaction path is S0- > TS2- > IN1 channel. The main effect of acid catalysis is to catalyze the dehydration reaction of sulfenic acid to form sulfur cations for subsequently ring closing reaction.
The structure of penicillin sulfoxide is rearranged to cephalosporins by the Morin rearrangement. It is a unit reaction for the preparation of various types of cephalosporins. In order to make better use of the reaction and in view of the shortage of the reaction theory, this study used m062x/6-311++G (d, p) to explore the possible ring-opening reaction of the penicillin sulfoxide. It is found that the isomer of (S)-sulfoxide is a necessary structure. At the same time, the intramolecular hydrogen bonding effect between the side-chain amide proton (-CONH-) and the sulfinyl oxygen (-SO) is the decisive structure factor for the formation of alkenyl in ring-opening reaction, and the best reaction path is S0- > TS2- > IN1 channel. The main effect of acid catalysis is to catalyze the dehydration reaction of sulfenic acid to form sulfur cations for subsequently ring closing reaction.
2020, 39(9): 1601-1614
doi: 10.14102/j.cnki.0254-5861.2011-2657
Abstract:
In this work, the structure of 4-((2R)-2-(3, 4-dibromophenyl)-1-fluorocyclopropyl)-N-(o-tolyl) benzamide (DBFB) has been determined at room temperature using single-crystal X-ray diffraction data. The structure of the compound was solved using 1464 observed reflections with I ≥ 2σ(I). It crystallizes in monoclinic space group P21 with a = 20.0820(10), b = 10.2770(10), c = 4.860(2) Å, β = 95.9600(10)°, V = 997.6(4) Å3, Z = 2, Dc = 1.675 g/m3, F(000) = 500, Μr = 503.18, μ = 4.09 mm-1 and the final R = 0.0639. The molecular packing of the title compound exhibits C–H⋅⋅⋅O and C–H⋅⋅⋅F hydrogen bonds forming a supramolecular network. Furthermore, conformational analysis has been performed in order to confirm the most stable conformer of the title compound. Geometrical parameters of the keto conformer in the ground state have been obtained using density functional theory (DFT) method with B3LYP/6-31G(d, p) level of theory. In general, a good agreement between the calculated and experimental results was observed. The normal modes of vibration, molecular boundary orbitals (HOMO and LUMO), reactivity descriptors, Mullikan atomic charges and molecular electrostatic potential for the title compound have been evaluated and discussed.
In this work, the structure of 4-((2R)-2-(3, 4-dibromophenyl)-1-fluorocyclopropyl)-N-(o-tolyl) benzamide (DBFB) has been determined at room temperature using single-crystal X-ray diffraction data. The structure of the compound was solved using 1464 observed reflections with I ≥ 2σ(I). It crystallizes in monoclinic space group P21 with a = 20.0820(10), b = 10.2770(10), c = 4.860(2) Å, β = 95.9600(10)°, V = 997.6(4) Å3, Z = 2, Dc = 1.675 g/m3, F(000) = 500, Μr = 503.18, μ = 4.09 mm-1 and the final R = 0.0639. The molecular packing of the title compound exhibits C–H⋅⋅⋅O and C–H⋅⋅⋅F hydrogen bonds forming a supramolecular network. Furthermore, conformational analysis has been performed in order to confirm the most stable conformer of the title compound. Geometrical parameters of the keto conformer in the ground state have been obtained using density functional theory (DFT) method with B3LYP/6-31G(d, p) level of theory. In general, a good agreement between the calculated and experimental results was observed. The normal modes of vibration, molecular boundary orbitals (HOMO and LUMO), reactivity descriptors, Mullikan atomic charges and molecular electrostatic potential for the title compound have been evaluated and discussed.
2020, 39(9): 1615-1626
doi: 10.14102/j.cnki.0254-5861.2011-2661
Abstract:
In this study, we explored a three-dimensional quantitative structure-activity relationship (3D-QSAR) model of 63 HBV viral gene expression inhibitors containing dihydroquinolizinones. Two high predictive QSAR models have been built, including comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA). The internal validation parameter (CoMFA, q2 = 0.701, r2 = 0.999; CoMSIA, q2 = 0.721, r2 = 0.998) and external validation parameter (CoMFA, rpred = 0.9992; CoMSIA, rpred = 0.9992) indicated that the models have good predictive abilities and significant statistical reliability. We designed several molecules with potentially higher predicted activity on the basis of the result of the models. This work might provide useful information to design novel HBV viral gene expression inhibitors.
In this study, we explored a three-dimensional quantitative structure-activity relationship (3D-QSAR) model of 63 HBV viral gene expression inhibitors containing dihydroquinolizinones. Two high predictive QSAR models have been built, including comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA). The internal validation parameter (CoMFA, q2 = 0.701, r2 = 0.999; CoMSIA, q2 = 0.721, r2 = 0.998) and external validation parameter (CoMFA, rpred = 0.9992; CoMSIA, rpred = 0.9992) indicated that the models have good predictive abilities and significant statistical reliability. We designed several molecules with potentially higher predicted activity on the basis of the result of the models. This work might provide useful information to design novel HBV viral gene expression inhibitors.
2020, 39(9): 1627-1632
doi: 10.14102/j.cnki.0254-5861.2011-2667
Abstract:
X2Ge=Sn: (X = H, Me, F, Cl, Br, Ph, Ar···) are new species of chemistry. The cycloaddition reaction of X2Ge=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X2Ge=Sn: and the symmetric π-bonded compounds, the cycloaddition reactions of Me2Ge=Sn: and ethylene were selected as model reactions in this paper, and the mechanism was investigated for the first time here using the MP2 theory together with the 6-311++G** basis set for C, H and Ge atoms and the LanL2dzbasis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule present is that the 5p unoccupied orbital of Sn in Me2Ge=Sn: and the π orbital of ethylene form a π → p donor–acceptor bond, resulting in an intermediate which, due to its instability, makes itself isomerize into a four-membered Ge-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Ge-heterocyclic ring stannylene and the π orbital of ethylene form a π → p donor-acceptor bond, the four-membered Ge-heterocyclic ring stannylene further combines with ethylene to get another intermediate. Because the Sn atom in this intermediate exhibits sp3 hybridization after transition state, the intermediate isomerizes to a Ge-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X2Ge=Sn: and the symmetric π-bonded compounds. This study opens up a new research field for stannylene chemistry.
X2Ge=Sn: (X = H, Me, F, Cl, Br, Ph, Ar···) are new species of chemistry. The cycloaddition reaction of X2Ge=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X2Ge=Sn: and the symmetric π-bonded compounds, the cycloaddition reactions of Me2Ge=Sn: and ethylene were selected as model reactions in this paper, and the mechanism was investigated for the first time here using the MP2 theory together with the 6-311++G** basis set for C, H and Ge atoms and the LanL2dzbasis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule present is that the 5p unoccupied orbital of Sn in Me2Ge=Sn: and the π orbital of ethylene form a π → p donor–acceptor bond, resulting in an intermediate which, due to its instability, makes itself isomerize into a four-membered Ge-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Ge-heterocyclic ring stannylene and the π orbital of ethylene form a π → p donor-acceptor bond, the four-membered Ge-heterocyclic ring stannylene further combines with ethylene to get another intermediate. Because the Sn atom in this intermediate exhibits sp3 hybridization after transition state, the intermediate isomerizes to a Ge-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X2Ge=Sn: and the symmetric π-bonded compounds. This study opens up a new research field for stannylene chemistry.
2020, 39(9): 1633-1638
doi: 10.14102/j.cnki.0254-5861.2011-2668
Abstract:
We report here a cocrystal with artesunate as the active pharmaceutical ingredient (API) and a pharmaceutical intermediate 4, 4΄-bipyridine as the cocrystal former (CCF). The analysis of single-crystal X-ray diffraction demonstrates that the eutectic structural unit consists of two artesunate molecules and one 4, 4΄-bipyridine molecule with their ratio to be 2:1. The carboxyl group on artesunate acts as a donor, and the acceptor is N on 4, 4΄-bipyridine, forming an O–H···N hydrogen bond. The appearance of new diffraction peaks in the X-ray powder diffraction pattern also indicates the formation of new phases. The PXRD results indicated a pure phase for the synthesized sample. The cocrystal is slightly soluble in water. Antimicrobial activities showed that the cocrystal displayed effective inhibition of different bacteria.
We report here a cocrystal with artesunate as the active pharmaceutical ingredient (API) and a pharmaceutical intermediate 4, 4΄-bipyridine as the cocrystal former (CCF). The analysis of single-crystal X-ray diffraction demonstrates that the eutectic structural unit consists of two artesunate molecules and one 4, 4΄-bipyridine molecule with their ratio to be 2:1. The carboxyl group on artesunate acts as a donor, and the acceptor is N on 4, 4΄-bipyridine, forming an O–H···N hydrogen bond. The appearance of new diffraction peaks in the X-ray powder diffraction pattern also indicates the formation of new phases. The PXRD results indicated a pure phase for the synthesized sample. The cocrystal is slightly soluble in water. Antimicrobial activities showed that the cocrystal displayed effective inhibition of different bacteria.
2020, 39(9): 1639-1654
doi: 10.14102/j.cnki.0254-5861.2011-2770
Abstract:
Three new acylhydrazones containing pyrazine ring (C12H11N5O2·CH3COOH, 1; C13H13N5O·2CH3COOH, 2; C13H13N5O3·C13H13N5O3, 3) were synthesized and fully characterized. The single-crystal XRD indicated that both 1 and 2 crystallized in monoclinic, P21/c space group but 3 belonged to monoclinic, C2/c space group. The temperature of the maximum thermal decomposition peaks measured by thermogravimetry for 1~3 is 284, 289 and 276 ℃ respectively, all showing better thermal stabilities. The interactions of 1~3 with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were studied by UV-Vis absorption spectroscopy and fluorescence spectroscopy, respectively, presenting that 1~3 could bind to CT-DNA via groove binding mode and quench the fluorescence of BSA through static process. Moreover, molecular docking studies of the interactions between 1~3 with DNA/BSA were in good agreement with experimental results. From antimicrobial activities of 1~3 and gentamycin sulfate against Staphylococcus aureus, Escherichia coli and Salmonella typhimurium, it was inferred that 3 had generally stronger antibacterial activity than 1 and 2 and is more active against Staphylococcus aureus than gentamycin sulfate. The cytotoxic tests of 1~3 and etoposide on human lung cancer cells (A549) were carried out by using the MTT method.
Three new acylhydrazones containing pyrazine ring (C12H11N5O2·CH3COOH, 1; C13H13N5O·2CH3COOH, 2; C13H13N5O3·C13H13N5O3, 3) were synthesized and fully characterized. The single-crystal XRD indicated that both 1 and 2 crystallized in monoclinic, P21/c space group but 3 belonged to monoclinic, C2/c space group. The temperature of the maximum thermal decomposition peaks measured by thermogravimetry for 1~3 is 284, 289 and 276 ℃ respectively, all showing better thermal stabilities. The interactions of 1~3 with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were studied by UV-Vis absorption spectroscopy and fluorescence spectroscopy, respectively, presenting that 1~3 could bind to CT-DNA via groove binding mode and quench the fluorescence of BSA through static process. Moreover, molecular docking studies of the interactions between 1~3 with DNA/BSA were in good agreement with experimental results. From antimicrobial activities of 1~3 and gentamycin sulfate against Staphylococcus aureus, Escherichia coli and Salmonella typhimurium, it was inferred that 3 had generally stronger antibacterial activity than 1 and 2 and is more active against Staphylococcus aureus than gentamycin sulfate. The cytotoxic tests of 1~3 and etoposide on human lung cancer cells (A549) were carried out by using the MTT method.
2020, 39(9): 1655-1661
doi: 10.14102/j.cnki.0254-5861.2011-2757
Abstract:
A new transition-metal-free protocol for the synthesis of polysubstituted 1,5-diketone derivatives from readily available starting materials has been developed. All the compounds were confirmed by HRMS, 1H NMR and 13C NMR, and the single crystal structure of compound 4f was determined to be of triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A new transition-metal-free protocol for the synthesis of polysubstituted 1,5-diketone derivatives from readily available starting materials has been developed. All the compounds were confirmed by HRMS, 1H NMR and 13C NMR, and the single crystal structure of compound 4f was determined to be of triclinic system, space group P
2020, 39(9): 1662-1668
doi: 10.14102/j.cnki.0254-5861.2011-2672
Abstract:
Solid oxide carbon dioxide electrolysers are expected to play a key role in carbon-neutral energy landscape. However, the limited activity of traditional ceramic cathodes still restricts the electrochemical performance. Here we report the doping of Mn at the B site of SrFeO3-δ cathode to improve CO2 electrolysis. The oxygen vacancy concentration is increased by ~30% with Mn doping while the surface oxygen exchange coefficients are enhanced by ~10 times. The chemisorption of CO2 indicates the presence of chemical intermediate state between CO2 molecule and carbonate ion on the oxygen-deficient cathode surface which therefore leads to the desorption temperature of ~800 ℃. The Mn-doped SrFeO3-δ enhances CO2 electrolysis with no performance degradation being observed even after high-temperature operation of 100 hours.
Solid oxide carbon dioxide electrolysers are expected to play a key role in carbon-neutral energy landscape. However, the limited activity of traditional ceramic cathodes still restricts the electrochemical performance. Here we report the doping of Mn at the B site of SrFeO3-δ cathode to improve CO2 electrolysis. The oxygen vacancy concentration is increased by ~30% with Mn doping while the surface oxygen exchange coefficients are enhanced by ~10 times. The chemisorption of CO2 indicates the presence of chemical intermediate state between CO2 molecule and carbonate ion on the oxygen-deficient cathode surface which therefore leads to the desorption temperature of ~800 ℃. The Mn-doped SrFeO3-δ enhances CO2 electrolysis with no performance degradation being observed even after high-temperature operation of 100 hours.
2020, 39(9): 1669-1674
doi: 10.14102/j.cnki.0254-5861.2011-2660
Abstract:
Bulky azole ligands in combination with PdCl2 provide three new palladium(Ⅱ) complexes. All these complexes, as pre-catalysts, have high catalytic efficiency for the Suzuki-Miyaura cross-coupling reactions of sterically hindered aryl chlorides and good to high yields are obtained with low catalysts loadings (0.1 mol%) under mild conditions in air.
Bulky azole ligands in combination with PdCl2 provide three new palladium(Ⅱ) complexes. All these complexes, as pre-catalysts, have high catalytic efficiency for the Suzuki-Miyaura cross-coupling reactions of sterically hindered aryl chlorides and good to high yields are obtained with low catalysts loadings (0.1 mol%) under mild conditions in air.
2020, 39(9): 1675-1688
doi: 10.14102/j.cnki.0254-5861.2011-2685
Abstract:
The g-C3N4/Ag/GO (CNAG) photocatalysts were synthesized by a facile two-step reaction route. The as-prepared CNAG samples were characterized by X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL) and ultraviolet-visible diffuse reflectance spectroscopy techniques (UV-vis DRS). The photocatalytic activity was obtained by degrading rhodamine B (RhB) under simulated sunlight and the results showed that photocatalytic activity of CNAG was much higher than that of pure g-C3N4 and g-C3N4/Ag. When the mass ratio of GO was 6%, the as-prepared CNAG-6% sample possessed the highest photocatalytic activity and the kinetic constant of RhB degradation was 0.077 min-1, which was almost 4.3 times higher than that of pure g-C3N4 (0.018 min-1) and 2.5 times higher than that of the g-C3N4/Ag (0.031 min-1) composite, respectively. The toxicity of CNAG samples was assessed via seed germination experiment and no significant inhibitory effect was observed. The enhanced photocatalytic activity could be attributed to the synergistic effect of partial surface plasma resonance (SPR) effect of Ag, strong visible light absorption and the high separation efficiency of photon-generated carrier. The CNAG-6% sample exhibited excellent stability during the cycle experiment. Finally, a possible photocatalytic mechanism was proposed.
The g-C3N4/Ag/GO (CNAG) photocatalysts were synthesized by a facile two-step reaction route. The as-prepared CNAG samples were characterized by X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL) and ultraviolet-visible diffuse reflectance spectroscopy techniques (UV-vis DRS). The photocatalytic activity was obtained by degrading rhodamine B (RhB) under simulated sunlight and the results showed that photocatalytic activity of CNAG was much higher than that of pure g-C3N4 and g-C3N4/Ag. When the mass ratio of GO was 6%, the as-prepared CNAG-6% sample possessed the highest photocatalytic activity and the kinetic constant of RhB degradation was 0.077 min-1, which was almost 4.3 times higher than that of pure g-C3N4 (0.018 min-1) and 2.5 times higher than that of the g-C3N4/Ag (0.031 min-1) composite, respectively. The toxicity of CNAG samples was assessed via seed germination experiment and no significant inhibitory effect was observed. The enhanced photocatalytic activity could be attributed to the synergistic effect of partial surface plasma resonance (SPR) effect of Ag, strong visible light absorption and the high separation efficiency of photon-generated carrier. The CNAG-6% sample exhibited excellent stability during the cycle experiment. Finally, a possible photocatalytic mechanism was proposed.
2020, 39(9): 1689-1693
doi: 10.14102/j.cnki.0254-5861.2011-2637
Abstract:
Hydrothermal reaction of Cu(NO3)2·3H2O and 4-(4-carboxyphenoxy)isophthalic acid (H3cpia) results in a two-dimensional coordination polymer based on paddle-wheel-like dinuclear clusters, namely [C60H54Cu4O39]n (1). Complex 1 is of triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
Hydrothermal reaction of Cu(NO3)2·3H2O and 4-(4-carboxyphenoxy)isophthalic acid (H3cpia) results in a two-dimensional coordination polymer based on paddle-wheel-like dinuclear clusters, namely [C60H54Cu4O39]n (1). Complex 1 is of triclinic system, space group P
2020, 39(9): 1694-1698
doi: 10.14102/j.cnki.0254-5861.2011-2646
Abstract:
A new selenite compound CdNi(SeO3)2(H2O)2 has been obtained by a conventional hydrothermal method. This compound crystallizes in monoclinic system of space group C2/c, which exhibits a layer structure built by NiO6 octahedra and SeO3 trigonal pyramids running along the a-axis. The layers show a unique eight-rings hole network. The compound is stable at room temperature while the loss of H2O molecules happens with heating above 523 K. Magnetic measurements indicate that CdNi(SeO3)2(H2O)2 is an antiferromagnet and possesses an antiferromagnetic ordering at TN = 15 K.
A new selenite compound CdNi(SeO3)2(H2O)2 has been obtained by a conventional hydrothermal method. This compound crystallizes in monoclinic system of space group C2/c, which exhibits a layer structure built by NiO6 octahedra and SeO3 trigonal pyramids running along the a-axis. The layers show a unique eight-rings hole network. The compound is stable at room temperature while the loss of H2O molecules happens with heating above 523 K. Magnetic measurements indicate that CdNi(SeO3)2(H2O)2 is an antiferromagnet and possesses an antiferromagnetic ordering at TN = 15 K.
2020, 39(9): 1699-1706
doi: 10.14102/j.cnki.0254-5861.2011-2639
Abstract:
Two Schiff bases (DAMBA-Fc and DAA-Fc) derived from dehydroabietic acid have been successfully synthesized and characterized by means of FT-IR, elemental analysis, HRMS, and NMR spectroscopy. The crystal structure of DAA-Fc can be determined by single-crystal X-ray diffraction. The compound is of monoclinic system, space group P21 with a = 10.7379(6), b = 7.5004(4), c = 33.3294(18) Å, β = 97.996(3)º, Z = 4, V = 2658.2(3) Å3, Mr = 481.48, Dc = 1.203 g/cm3, S = 1.034, μ = 0.585 mm-1, F(000) = 1032, the final R = 0.0566 and wR = 0.0701 for 5645 observed reflections (I > 2σ(I)). In addition, cyclic and differential pulse voltammogram techniques have been applied to differentiate the redox properties of the aromatic- and aliphatic-connected Schiff bases DAMBA-Fc and DAA-Fc, respectively.
Two Schiff bases (DAMBA-Fc and DAA-Fc) derived from dehydroabietic acid have been successfully synthesized and characterized by means of FT-IR, elemental analysis, HRMS, and NMR spectroscopy. The crystal structure of DAA-Fc can be determined by single-crystal X-ray diffraction. The compound is of monoclinic system, space group P21 with a = 10.7379(6), b = 7.5004(4), c = 33.3294(18) Å, β = 97.996(3)º, Z = 4, V = 2658.2(3) Å3, Mr = 481.48, Dc = 1.203 g/cm3, S = 1.034, μ = 0.585 mm-1, F(000) = 1032, the final R = 0.0566 and wR = 0.0701 for 5645 observed reflections (I > 2σ(I)). In addition, cyclic and differential pulse voltammogram techniques have been applied to differentiate the redox properties of the aromatic- and aliphatic-connected Schiff bases DAMBA-Fc and DAA-Fc, respectively.
2020, 39(9): 1707-1713
doi: 10.14102/j.cnki.0254-5861.2011-2647
Abstract:
The title compound cytosinium isophthalate (C-H2IA) self-assembly of cytosine (C) and isophthalic acid (H2IA) in aqueous media has been synthesized and the crystal structure with a reasonable protonation state is redetermined. Single-crystal X-ray diffraction analysis reveals that each asymmetric unit contains one protoned cytosine molecule and one deprotoned isophthalic acid. The proton transferred from carboxylic acid to the pyrimidine ring is disordered across an inversion center with occupancy of 0.5 and the proton located to one of the carboxylate group lies on an inversion center shared by two crystallographically equivalent oxygen atoms. In addition, the cytosine molecules are connected by complementary hydrogen bonds to form a one-dimensional tape structure. The neighboring isophthalic acids are connected via hydrogen bonds between carboxyl groups to form a one-dimensional lattice like tape. Furthermore, the adjacent organic base tapes and organic acid tapes are stacked one with another through π-π stacking interactions to form a three-dimensional supramolecular structure. Interestingly, C-H2IA displays a green phosphorescence in solid state at room temperature with the lifetime of 0.7 s determined by time resolved studies, indicating that supramolecular C-H2IA is a potential pure organic phosphorescent luminogens.
The title compound cytosinium isophthalate (C-H2IA) self-assembly of cytosine (C) and isophthalic acid (H2IA) in aqueous media has been synthesized and the crystal structure with a reasonable protonation state is redetermined. Single-crystal X-ray diffraction analysis reveals that each asymmetric unit contains one protoned cytosine molecule and one deprotoned isophthalic acid. The proton transferred from carboxylic acid to the pyrimidine ring is disordered across an inversion center with occupancy of 0.5 and the proton located to one of the carboxylate group lies on an inversion center shared by two crystallographically equivalent oxygen atoms. In addition, the cytosine molecules are connected by complementary hydrogen bonds to form a one-dimensional tape structure. The neighboring isophthalic acids are connected via hydrogen bonds between carboxyl groups to form a one-dimensional lattice like tape. Furthermore, the adjacent organic base tapes and organic acid tapes are stacked one with another through π-π stacking interactions to form a three-dimensional supramolecular structure. Interestingly, C-H2IA displays a green phosphorescence in solid state at room temperature with the lifetime of 0.7 s determined by time resolved studies, indicating that supramolecular C-H2IA is a potential pure organic phosphorescent luminogens.
2020, 39(9): 1714-1722
doi: 10.14102/j.cnki.0254-5861.2011-2666
Abstract:
In this work, a cis-dicyanoiron(Ⅱ) building block, cis-FeⅡ(bpy)2(CN)2 (1, bpy = 2,2΄-bipyridine), has been prepared and fully characterized by IR, electronic absorption spectra, elemental analysis, cyclic voltammetry and single-crystal X-ray diffraction analysis. The interactions of complex 1 with selected metal ions, such as Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ), were investigated employing electronic absorption spectroscopy. The electronic absorption spectroscopy indicates Cu(Ⅱ), Fe(Ⅲ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) ions steadily coordinate with 1 via cyanide, respectively. Fluorescent emission intensity of 1 increased upon the addition of Zn(Ⅱ) ion, quenched by adding ions Cu(Ⅱ), Fe(Ⅲ) and Pb(Ⅱ), and it was almost unchanged when adding the Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ) ions.
In this work, a cis-dicyanoiron(Ⅱ) building block, cis-FeⅡ(bpy)2(CN)2 (1, bpy = 2,2΄-bipyridine), has been prepared and fully characterized by IR, electronic absorption spectra, elemental analysis, cyclic voltammetry and single-crystal X-ray diffraction analysis. The interactions of complex 1 with selected metal ions, such as Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ), were investigated employing electronic absorption spectroscopy. The electronic absorption spectroscopy indicates Cu(Ⅱ), Fe(Ⅲ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) ions steadily coordinate with 1 via cyanide, respectively. Fluorescent emission intensity of 1 increased upon the addition of Zn(Ⅱ) ion, quenched by adding ions Cu(Ⅱ), Fe(Ⅲ) and Pb(Ⅱ), and it was almost unchanged when adding the Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ) ions.
2020, 39(9): 1723-1728
doi: 10.14102/j.cnki.0254-5861.2011-2683
Abstract:
A new dichlorobridged dimeric Cu(Ⅱ) complex bearing 2,2΄-(1H-1,2,4-triazole-1,3-diyl)dipyridine ligands has been synthesized. Its structure has been characterized by X-ray single-crystal diffraction. New Cu(Ⅱ) complex crystallizes in triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A new dichlorobridged dimeric Cu(Ⅱ) complex bearing 2,2΄-(1H-1,2,4-triazole-1,3-diyl)dipyridine ligands has been synthesized. Its structure has been characterized by X-ray single-crystal diffraction. New Cu(Ⅱ) complex crystallizes in triclinic system, space group P
2020, 39(9): 1729-1734
doi: 10.14102/j.cnki.0254-5861.2011-2691
Abstract:
A three-dimensional coordination polymer, [Zn2(L)2(bpp)(H2O)2]n (H2L = 2,5-dicarboxylic acid-3,4-ethylene dioxythiophene, bpp = 1,3-di(4-pyridyl)propane), was synthesized with high yield under solvothermal reaction conditions and structurally characterized by elemental analysis, infrared spectra, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction analysis. It crystallizes in orthorhombic space group Pnma with a = 16.6542(9), b = 18.0868(10), c = 10.7528(5) Å, V = 3239.0(3) Å3, Z = 4, Dc = 1.684 g/cm3, Mr = 821.38, Dc = 1.684 g/cm3, µ = 1.683 mm−1, F(000) = 1672, R = 0.0466, wR = 0.0933 and S = 1.066. The compound exhibits a three-dimensional structure, which can be simplified into a 2-fold interpenetrated pcu topological network. Moreover, it displays luminescence emission in the solid state at room temperature.
A three-dimensional coordination polymer, [Zn2(L)2(bpp)(H2O)2]n (H2L = 2,5-dicarboxylic acid-3,4-ethylene dioxythiophene, bpp = 1,3-di(4-pyridyl)propane), was synthesized with high yield under solvothermal reaction conditions and structurally characterized by elemental analysis, infrared spectra, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction analysis. It crystallizes in orthorhombic space group Pnma with a = 16.6542(9), b = 18.0868(10), c = 10.7528(5) Å, V = 3239.0(3) Å3, Z = 4, Dc = 1.684 g/cm3, Mr = 821.38, Dc = 1.684 g/cm3, µ = 1.683 mm−1, F(000) = 1672, R = 0.0466, wR = 0.0933 and S = 1.066. The compound exhibits a three-dimensional structure, which can be simplified into a 2-fold interpenetrated pcu topological network. Moreover, it displays luminescence emission in the solid state at room temperature.
2020, 39(9): 1735-1739
doi: 10.14102/j.cnki.0254-5861.2011-2697
Abstract:
A new Cu(Ⅰ) coordination polymer, [Cu4(MA)2(HCA)2]n (1, MA = melamine, H3CA = cyanuric acid), has been synthesized under hydrothermal conditions using CuCl2·2H2O and MA as the starting materials. Interestingly, cyanuric acid was obtained by the in situ hydrolysis and the deaminization of melamine, and the Cu(Ⅰ) ion was obtained by the in situ reduction of Cu(Ⅱ) ion during the self-assembly process. The crystal structure is of monoclinic, space group Pc with a = 3.539(3), b = 22.377(2), c = 15.844(1) Å, β = 90.723(1)º, V = 1254.6(2) Å3, C12H14Cu4N18O6, Mr = 760.61, Z = 2, Dc = 2.013 g/cm3, F(000) = 752, μ = 3.426 mm-1, R = 0.0479 and wR = 0.1243 for 3172 observed reflections (I > 2σ(I)). The crystal structural analysis revealed that the cooperation of coordinate-covalent bonds, intermolecular hydrogen bonds and π-π interactions give rise to a 3D supramolecular framework with 5-connected BN topology. Moreover, the thermal stability and luminescent property of 1 were also investigated.
A new Cu(Ⅰ) coordination polymer, [Cu4(MA)2(HCA)2]n (1, MA = melamine, H3CA = cyanuric acid), has been synthesized under hydrothermal conditions using CuCl2·2H2O and MA as the starting materials. Interestingly, cyanuric acid was obtained by the in situ hydrolysis and the deaminization of melamine, and the Cu(Ⅰ) ion was obtained by the in situ reduction of Cu(Ⅱ) ion during the self-assembly process. The crystal structure is of monoclinic, space group Pc with a = 3.539(3), b = 22.377(2), c = 15.844(1) Å, β = 90.723(1)º, V = 1254.6(2) Å3, C12H14Cu4N18O6, Mr = 760.61, Z = 2, Dc = 2.013 g/cm3, F(000) = 752, μ = 3.426 mm-1, R = 0.0479 and wR = 0.1243 for 3172 observed reflections (I > 2σ(I)). The crystal structural analysis revealed that the cooperation of coordinate-covalent bonds, intermolecular hydrogen bonds and π-π interactions give rise to a 3D supramolecular framework with 5-connected BN topology. Moreover, the thermal stability and luminescent property of 1 were also investigated.
