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2020 Volume 39 Issue 4
2020, 39(4): 605-614
doi: 10.14102/j.cnki.0254-5861.2011-2819
Abstract:
Electrochemical quartz crystal microbalance (EQCM) is a powerful tool to study the mass change and charge transfer during electrochemical process. The mass change on the electrode surface can be monitored with high precision and high sensitivity, making it possible to analyze the in-depth mechanism of electrode reactions. The application of metal anodes has exhibited great potential for the future energy storage devices for the elevated capacity. Herein, we review the research progress utilizing EQCM for metal anodes, including the deposition/dissolution process, the side reactions, the effect of additives, etc. Furthermore, we also put forward a perspective on research of the mechanism and performance improvement of metal anodes.
Electrochemical quartz crystal microbalance (EQCM) is a powerful tool to study the mass change and charge transfer during electrochemical process. The mass change on the electrode surface can be monitored with high precision and high sensitivity, making it possible to analyze the in-depth mechanism of electrode reactions. The application of metal anodes has exhibited great potential for the future energy storage devices for the elevated capacity. Herein, we review the research progress utilizing EQCM for metal anodes, including the deposition/dissolution process, the side reactions, the effect of additives, etc. Furthermore, we also put forward a perspective on research of the mechanism and performance improvement of metal anodes.
2020, 39(4): 615-622
doi: 10.14102/j.cnki.0254-5861.2011-2826
Abstract:
The traditional strengthening elements of titanium alloys include Al, Mo, V, etc., however, the high cost and toxicity of these elements put a limit on their further applications for biomaterials. Ubiquitous light elements such as oxygen are hopeful replacement due to high biocompatibility. It is recognized that the oxygen enhances the strength but pays the price of brittleness, thus the amount of oxygen is constrained. However, recent study results indicated that excess oxygen can keep high ductility together with high strength of titanium. This paper reviews the influence and the mechanism of oxygen on the strength and ductility of titanium alloys, and provides a new perspective for the strengthening method of titanium alloys.
The traditional strengthening elements of titanium alloys include Al, Mo, V, etc., however, the high cost and toxicity of these elements put a limit on their further applications for biomaterials. Ubiquitous light elements such as oxygen are hopeful replacement due to high biocompatibility. It is recognized that the oxygen enhances the strength but pays the price of brittleness, thus the amount of oxygen is constrained. However, recent study results indicated that excess oxygen can keep high ductility together with high strength of titanium. This paper reviews the influence and the mechanism of oxygen on the strength and ductility of titanium alloys, and provides a new perspective for the strengthening method of titanium alloys.
2020, 39(4): 623-629
doi: 10.14102/j.cnki.0254-5861.2011-2824
Abstract:
A nanosecond pulse laser source head (Nd: YAG laser, Inlite Ⅱ-20, Continuum) was equipped to a high-voltage electron microscope (HVEM, Hitachi, H-1300) to develop a laser-HVEM system at Hokkaido University. Using the laser-HVEM, new methods for in-situ observation on the formation process of laser-induced lattice point defects at the internal of crystalline solid are achieved; some striking phenomena and potential mechanisms are explored. In the present paper, we review our progresses on in-situ experiments of lattice defects behavior in metal using the laser-HVEM. These progresses are expected to provide insight for a broader application of laser-HVEM in scientific research.
A nanosecond pulse laser source head (Nd: YAG laser, Inlite Ⅱ-20, Continuum) was equipped to a high-voltage electron microscope (HVEM, Hitachi, H-1300) to develop a laser-HVEM system at Hokkaido University. Using the laser-HVEM, new methods for in-situ observation on the formation process of laser-induced lattice point defects at the internal of crystalline solid are achieved; some striking phenomena and potential mechanisms are explored. In the present paper, we review our progresses on in-situ experiments of lattice defects behavior in metal using the laser-HVEM. These progresses are expected to provide insight for a broader application of laser-HVEM in scientific research.
2020, 39(4): 630-642
doi: 10.14102/j.cnki.0254-5861.2011-2468
Abstract:
The C–C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the [Rh(R,S-L)]+ complex producing the R,S-, S,R-, R,R- and S,S-product were investigated systematically at the BP86/6-31G(d,p) level in gas phase and THF, and the R,S- and S,R-reaction pathways were revisited at the M062X/6-31G(d,p) level in THF. The computational results reveal that THF only marginally alters the free-energy barriers, but elevates the relative energies of all species. The BP86 functional testifies that in both gas phase and THF, the activation of strained C–C bonds bears relatively low free-energy barriers, and the rate-determining steps of S,R- and R,R-channels are different from those of R,S- and S,S-channels. The BP86 functional also predicts that the R,S-channel is energetically most favorable in gas phase, but the S,R-product is dominant in THF. The change of NPA charges can mirror the variation of molecular structures to elucidate reaction mechanisms.
The C–C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the [Rh(R,S-L)]+ complex producing the R,S-, S,R-, R,R- and S,S-product were investigated systematically at the BP86/6-31G(d,p) level in gas phase and THF, and the R,S- and S,R-reaction pathways were revisited at the M062X/6-31G(d,p) level in THF. The computational results reveal that THF only marginally alters the free-energy barriers, but elevates the relative energies of all species. The BP86 functional testifies that in both gas phase and THF, the activation of strained C–C bonds bears relatively low free-energy barriers, and the rate-determining steps of S,R- and R,R-channels are different from those of R,S- and S,S-channels. The BP86 functional also predicts that the R,S-channel is energetically most favorable in gas phase, but the S,R-product is dominant in THF. The change of NPA charges can mirror the variation of molecular structures to elucidate reaction mechanisms.
2020, 39(4): 643-650
doi: 10.14102/j.cnki.0254-5861.2011-2501
Abstract:
At the B3PW91/6-311+G(d,p)//MP2/6-311+G(d,p) level, molecular densities, detonation velocities, and detonation pressures of nitroso substituted derivatives of azetidine with their thermal stabilities were investigated to look for high energy density compounds (HEDCs). It was found that the azetidine derivatives had high heat of formation (HOF) and large bond dissociation energy (BDE). Intramolecular hydrogen bonds were located in three molecules (1, 4, and 5), and the molecular stability were improved markedly as well. For 5 and 6, the detonation performances (D= 9.36km/s and 10.80km/s, P= 44.42GPa and 60.70GPa, respectively) meet requirements as high energy density compounds. This work may provide basic information for further study of title compounds.
At the B3PW91/6-311+G(d,p)//MP2/6-311+G(d,p) level, molecular densities, detonation velocities, and detonation pressures of nitroso substituted derivatives of azetidine with their thermal stabilities were investigated to look for high energy density compounds (HEDCs). It was found that the azetidine derivatives had high heat of formation (HOF) and large bond dissociation energy (BDE). Intramolecular hydrogen bonds were located in three molecules (1, 4, and 5), and the molecular stability were improved markedly as well. For 5 and 6, the detonation performances (D= 9.36km/s and 10.80km/s, P= 44.42GPa and 60.70GPa, respectively) meet requirements as high energy density compounds. This work may provide basic information for further study of title compounds.
2020, 39(4): 651-661
doi: 10.14102/j.cnki.0254-5861.2011-2508
Abstract:
In order to understand the chemical-biological interactions governing their activities toward neuraminidase (NA), QSAR models of 28 thiazolidine-4-carboxylic acid derivatives with inhibitory influenza A virus were developed. Here a quantitative structure activity relationship (QSAR) model was built by three-dimensional holographic atomic vector field (3D-HoVAIF) and multiple linear regression (MLR). The estimation stability and prediction ability of the model were strictly analyzed by both internal and external validations. The correlation coefficient (R2) of established MLR model was 0.984, and the cross-validated correlation coefficient (Q2) of MLR model was 0.947. Furthermore, the cross-validated correlation coefficient for the test set (Qext2) was 0.967. The binding mode pattern of the compounds to the binding site of integrase enzyme was confirmed by docking studies. The results of present study indicated that this model can aid in designing more potent neuraminidase inhibitors.
In order to understand the chemical-biological interactions governing their activities toward neuraminidase (NA), QSAR models of 28 thiazolidine-4-carboxylic acid derivatives with inhibitory influenza A virus were developed. Here a quantitative structure activity relationship (QSAR) model was built by three-dimensional holographic atomic vector field (3D-HoVAIF) and multiple linear regression (MLR). The estimation stability and prediction ability of the model were strictly analyzed by both internal and external validations. The correlation coefficient (R2) of established MLR model was 0.984, and the cross-validated correlation coefficient (Q2) of MLR model was 0.947. Furthermore, the cross-validated correlation coefficient for the test set (Qext2) was 0.967. The binding mode pattern of the compounds to the binding site of integrase enzyme was confirmed by docking studies. The results of present study indicated that this model can aid in designing more potent neuraminidase inhibitors.
2020, 39(4): 662-672
doi: 10.14102/j.cnki.0254-5861.2011-2514
Abstract:
Polymorph screening is currently one of the most important strategies of innovators and generic companies from both pharmaceutical and intellectual property rights perspectives. Different polymorphs may have varying physicochemical properties which influence the bioavailability. The purpose of this study was to investigate the crystal structures and physicochemical properties of Nomegestrol acetate (NOMAC) polymorphs. Forms Ⅰ and Ⅱ (dioxane solvate) were isolated and prepared by systemic crystallization screening in this study, and the forms are reported for the first time. A structural analysis and comparison of all the forms are presented. This study was also the first time to apply a rapid and feasible ultra-high-performance-liquid chromatography (UHPLC)-electrospray ionization (ESI)-tandem mass spectrometry (MS) method to determine plasma levels of NOMAC within 3.0 mins. And this study demonstrated that the optimal crystal Form Ⅰ displayed higher bioavailability than API indicating that Form Ⅰ could be an alternative solid form that needs further research.
Polymorph screening is currently one of the most important strategies of innovators and generic companies from both pharmaceutical and intellectual property rights perspectives. Different polymorphs may have varying physicochemical properties which influence the bioavailability. The purpose of this study was to investigate the crystal structures and physicochemical properties of Nomegestrol acetate (NOMAC) polymorphs. Forms Ⅰ and Ⅱ (dioxane solvate) were isolated and prepared by systemic crystallization screening in this study, and the forms are reported for the first time. A structural analysis and comparison of all the forms are presented. This study was also the first time to apply a rapid and feasible ultra-high-performance-liquid chromatography (UHPLC)-electrospray ionization (ESI)-tandem mass spectrometry (MS) method to determine plasma levels of NOMAC within 3.0 mins. And this study demonstrated that the optimal crystal Form Ⅰ displayed higher bioavailability than API indicating that Form Ⅰ could be an alternative solid form that needs further research.
2020, 39(4): 673-681
doi: 10.14102/j.cnki.0254-5861.2011-2522
Abstract:
Two dibenzyltin compounds, {[C6H5O(O)C=N–N=C(Ph)COO] (m-Cl–C6H4CH2)2-Sn(CH3OH)}2 (1) and {[p-Me–C6H4O(O)C=N–N=C(Ph)COO] (m-Cl–C6H4CH2)2Sn(CH3OH)}2 (2), have been synthesized by microwave "one pot" reaction with benzoylhydrazine (or p-methyl benzhydrazine), phenylglyoxylic acid and di-m-chlorobenzyltin dichloride. Compound 2 contains two crystals 2a and 2b. The compounds have been characterized with IR, elemental analysis, 1H, 13C and 119Sn NMR spectra, H RMS. Three crystals are all binuclear molecules with a Sn2O2 four-membered ring plane, and each Sn atom center is seven-coordinated with [SnO4C2N] to form a distorted pentagonal bipyramidal configuration. In vitro antitumor activities of all compounds and carboplatin were evaluated by MTT against three human cancer cells such as NCI-H460 (lung cancer cells), HepG2 (liver cancer cells) and MCF7 (breast cancer cells), and compound 2 exhibited better antitumor activity.
Two dibenzyltin compounds, {[C6H5O(O)C=N–N=C(Ph)COO] (m-Cl–C6H4CH2)2-Sn(CH3OH)}2 (1) and {[p-Me–C6H4O(O)C=N–N=C(Ph)COO] (m-Cl–C6H4CH2)2Sn(CH3OH)}2 (2), have been synthesized by microwave "one pot" reaction with benzoylhydrazine (or p-methyl benzhydrazine), phenylglyoxylic acid and di-m-chlorobenzyltin dichloride. Compound 2 contains two crystals 2a and 2b. The compounds have been characterized with IR, elemental analysis, 1H, 13C and 119Sn NMR spectra, H RMS. Three crystals are all binuclear molecules with a Sn2O2 four-membered ring plane, and each Sn atom center is seven-coordinated with [SnO4C2N] to form a distorted pentagonal bipyramidal configuration. In vitro antitumor activities of all compounds and carboplatin were evaluated by MTT against three human cancer cells such as NCI-H460 (lung cancer cells), HepG2 (liver cancer cells) and MCF7 (breast cancer cells), and compound 2 exhibited better antitumor activity.
2020, 39(4): 682-692
doi: 10.14102/j.cnki.0254-5861.2011-2528
Abstract:
Two novel bis(2-hydroxy-5-R-benzylidene) carbohydrazide dibutyltin complexes (R: Cl (T1), Me (T2)) with hexanuclear and triangular frame structures were obtained by microwave-assisted solvothermal reaction of dibutyltin oxide precursor with the ligands in methanol environments, However, their structures are characterized by elemental analysis, IR, (1H, 13C) NMR spectra, and the molecular structures of T1 and T2 were confirmed by X-ray diffraction. The crystal of T1 belongs to triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
Two novel bis(2-hydroxy-5-R-benzylidene) carbohydrazide dibutyltin complexes (R: Cl (T1), Me (T2)) with hexanuclear and triangular frame structures were obtained by microwave-assisted solvothermal reaction of dibutyltin oxide precursor with the ligands in methanol environments, However, their structures are characterized by elemental analysis, IR, (1H, 13C) NMR spectra, and the molecular structures of T1 and T2 were confirmed by X-ray diffraction. The crystal of T1 belongs to triclinic system, space group P
2020, 39(4): 693-697
doi: 10.14102/j.cnki.0254-5861.2011-2464
Abstract:
An AIE-active azine derivative (1) was facilely synthesized by aldehyde-amine condensation of 2-hydroxy-1-naphthaldehyde and 3-methyl-2-benzothiazolinone hydrazone. It crystallizes in the monoclinic space group P21/n with a = 8.2176(5), b = 13.1733(7), c =14.5731(8) Å, β = 90.521(5)º, and Z = 4. Compound 1 exhibits aggregation-induced emission characteristics. In dilute solution, it is non-emissive, while strong emission was observed in the aqueous medium as a result of the molecular aggregation in poor solvent. The powder and crystals of 1 also exhibit strong fluorescence. In its crystal lattice, the molecules stack in a face-to-face style, but there is no π-π stacking interaction due to the long distance between adjacent molecules. It is the loose stacking mode that blocks the nonradiative decay channel resulting in its AIE effect.
An AIE-active azine derivative (1) was facilely synthesized by aldehyde-amine condensation of 2-hydroxy-1-naphthaldehyde and 3-methyl-2-benzothiazolinone hydrazone. It crystallizes in the monoclinic space group P21/n with a = 8.2176(5), b = 13.1733(7), c =14.5731(8) Å, β = 90.521(5)º, and Z = 4. Compound 1 exhibits aggregation-induced emission characteristics. In dilute solution, it is non-emissive, while strong emission was observed in the aqueous medium as a result of the molecular aggregation in poor solvent. The powder and crystals of 1 also exhibit strong fluorescence. In its crystal lattice, the molecules stack in a face-to-face style, but there is no π-π stacking interaction due to the long distance between adjacent molecules. It is the loose stacking mode that blocks the nonradiative decay channel resulting in its AIE effect.
2020, 39(4): 698-708
doi: 10.14102/j.cnki.0254-5861.2011-2494
Abstract:
For the reported chemical structures, the disordered fragments of the structure acting as hosts and guests are common and unmanageable for crystallographers. How to analyze and treat such disordered assemblies is an important task for crystallographers. It is often difficult for some researchers to refine the disordered structures, even to mechanically justify the refined consequence in the absence of expertise. Herein, some examples of disorder refinements selected from the literature, including the disordered assemblies of nitrate, perchlorate, alkyl, aromatic assemblies, and guest solvent molecules, are summarized and discussed to provide practical advice for investigating the disorders for crystallographic researchers and beginners. The refinement approach for these disordered assemblies is also discussed in detail, which is helpful for crystallographers.
For the reported chemical structures, the disordered fragments of the structure acting as hosts and guests are common and unmanageable for crystallographers. How to analyze and treat such disordered assemblies is an important task for crystallographers. It is often difficult for some researchers to refine the disordered structures, even to mechanically justify the refined consequence in the absence of expertise. Herein, some examples of disorder refinements selected from the literature, including the disordered assemblies of nitrate, perchlorate, alkyl, aromatic assemblies, and guest solvent molecules, are summarized and discussed to provide practical advice for investigating the disorders for crystallographic researchers and beginners. The refinement approach for these disordered assemblies is also discussed in detail, which is helpful for crystallographers.
2020, 39(4): 709-717
doi: 10.14102/j.cnki.0254-5861.2011-2488
Abstract:
Polymorphic structures of cyclometalated cationic Pt(Ⅱ)-isocyanide complexes (–)-1 [Pt((−)-NNC)(Dmpi)]Cl with different packing modes can be isolated before. In this paper, a series of solid-state powders with variable colors (yellow, orange and red) have been obtained from the evaporation of complex (–)-1 in different solvents. The crystallinity, thermogravimetric properties, absorption, luminescence and excited state lifetimes have been studied. In addition, intermolecular Pt···Pt interactions in the optimized configurations of different aggregates have been explored, and calculations of frontier molecular orbitals of monomer, dimer, trimer and tetramer have been carried out.
Polymorphic structures of cyclometalated cationic Pt(Ⅱ)-isocyanide complexes (–)-1 [Pt((−)-NNC)(Dmpi)]Cl with different packing modes can be isolated before. In this paper, a series of solid-state powders with variable colors (yellow, orange and red) have been obtained from the evaporation of complex (–)-1 in different solvents. The crystallinity, thermogravimetric properties, absorption, luminescence and excited state lifetimes have been studied. In addition, intermolecular Pt···Pt interactions in the optimized configurations of different aggregates have been explored, and calculations of frontier molecular orbitals of monomer, dimer, trimer and tetramer have been carried out.
2020, 39(4): 718-726
doi: 10.14102/j.cnki.0254-5861.2011-2617
Abstract:
A rare doubly-interpenetrating Zn-MOF (complex 1), formulated as {[Zn(tci)-(bpy)(NO3)·DMF·0.5CH3CN}n (H3tci = tri(2-carboxyethyl) isocyanurate, bpy = 4,4-bipyridine), has been constructed under solvothermal conditions and characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). 1 crystallizes in monoclinic system, space group C2/c with a = 21.5759(4), b = 12.87221(18), c = 26.4917(5) Å, β = 109.462(2)°, V = 6937.1(2) Å3, C50H56N14O27Zn4, Mr = 1546.56, Z = 4, Dc = 1.481 g·cm-3, μ = 2.325 mm-1 λ = 1.54178 Å, F(000) = 3160, S = 1.041, R = 0.0621 and wR = 0.1773. 1 features a two-fold interpenetrating 3D hms topology. Moreover, the thermal stabilities, fluorescent and CO2 adsorption properties were investigated. Complex 1 showed highly encouraging photocatalytic degradation of toxic dye molecules with a potential application in wastewater purification.
A rare doubly-interpenetrating Zn-MOF (complex 1), formulated as {[Zn(tci)-(bpy)(NO3)·DMF·0.5CH3CN}n (H3tci = tri(2-carboxyethyl) isocyanurate, bpy = 4,4-bipyridine), has been constructed under solvothermal conditions and characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). 1 crystallizes in monoclinic system, space group C2/c with a = 21.5759(4), b = 12.87221(18), c = 26.4917(5) Å, β = 109.462(2)°, V = 6937.1(2) Å3, C50H56N14O27Zn4, Mr = 1546.56, Z = 4, Dc = 1.481 g·cm-3, μ = 2.325 mm-1 λ = 1.54178 Å, F(000) = 3160, S = 1.041, R = 0.0621 and wR = 0.1773. 1 features a two-fold interpenetrating 3D hms topology. Moreover, the thermal stabilities, fluorescent and CO2 adsorption properties were investigated. Complex 1 showed highly encouraging photocatalytic degradation of toxic dye molecules with a potential application in wastewater purification.
2020, 39(4): 727-736
doi: 10.14102/j.cnki.0254-5861.2011-2483
Abstract:
0D dinuclear manganese(Ⅱ) coordination compound and 1D chain manganese(Ⅱ) coordination polymer, namely [Mn2(μ-L)(phen)4]·4H2O (1) and {[Mn2(μ5-L)(phen)2]·H2O}n (2), have been constructed hydrothermally using H4L (H4L = 2,3,3΄,4΄-diphenyl ether tetracarboxylic acid), phen (phen = 1,10-phenanthroline), and manganese chloride at 120 and 160 ℃, respectively. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P\begin{document}$ \overline 1 $\end{document}
0D dinuclear manganese(Ⅱ) coordination compound and 1D chain manganese(Ⅱ) coordination polymer, namely [Mn2(μ-L)(phen)4]·4H2O (1) and {[Mn2(μ5-L)(phen)2]·H2O}n (2), have been constructed hydrothermally using H4L (H4L = 2,3,3΄,4΄-diphenyl ether tetracarboxylic acid), phen (phen = 1,10-phenanthroline), and manganese chloride at 120 and 160 ℃, respectively. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA), and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P
2020, 39(4): 737-746
doi: 10.14102/j.cnki.0254-5861.2011-2484
Abstract:
Nd2Cu2O4+δ nanosheets were synthesized via coordination complex method (CCM) by using [NdCu(3,4-pdc)2(OAc)(H2O)5]·6.5H2O (1,3,4-pdc = 3,4-pyridinedicarboxylic acid) as the precursor. Compared to the particles prepared by SSM (simple solution method), Nd2Cu2O4+δ prepared by CCM showed leaf-like morphology composed of nanosheets with an average thickness of 50~80 nm and a BET surface area up to 17.9 m2/g. The Nd2Cu2O4+δ samples exhibit selective adsorption towards malachite green (MG) with significant Qm (maximum adsorption capacity) values reaching up 1.55 g/g at room temperature, and the thermodynamic parameters of adsorption process were obtained. In addition, the properties of selective adsorption of the prepared samples were investigated by temperature change tests.
Nd2Cu2O4+δ nanosheets were synthesized via coordination complex method (CCM) by using [NdCu(3,4-pdc)2(OAc)(H2O)5]·6.5H2O (1,3,4-pdc = 3,4-pyridinedicarboxylic acid) as the precursor. Compared to the particles prepared by SSM (simple solution method), Nd2Cu2O4+δ prepared by CCM showed leaf-like morphology composed of nanosheets with an average thickness of 50~80 nm and a BET surface area up to 17.9 m2/g. The Nd2Cu2O4+δ samples exhibit selective adsorption towards malachite green (MG) with significant Qm (maximum adsorption capacity) values reaching up 1.55 g/g at room temperature, and the thermodynamic parameters of adsorption process were obtained. In addition, the properties of selective adsorption of the prepared samples were investigated by temperature change tests.
2020, 39(4): 747-755
doi: 10.14102/j.cnki.0254-5861.2011-2486
Abstract:
By means of solvothermal reactions, a novel lanthanide-mercury compound, {[Ho(IA)3(H3O)2]2n[2n(HgCl4)][n(HgCl5)]}·3nH3O·nH2O (1, HIA = isonicotinc acid) was prepared and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2147(5), b = 20.8106(4), c = 15.3060(3) Å, β = 128.326(2)°, V = 6050.8(2) Å3, C36H45Cl13Hg3Ho2N6O20, Mr = 2274.26, Z = 4, Dc = 2.497 g/cm3, μ(MoKα) = 10.817 mm–1 and F(000) = 4232. It exhibits a one-dimensional (1-D) chain-like structure. Solid-state photoluminescence measurement shows that it displays brown light emission bands. These emission bands originate from the characteristic emissions of the 4f electrons intrashell transitions of 5S2 → 5I8 and 5F5 → 5I8 of the holmium(Ⅲ) ions in 1. The photoluminescence emission energy transfer mechanism is elucidated by the energy level diagrams of the holmium(Ⅲ) ions and isonicotinic acid ligand. Complex 1 has CIE chromaticity coordinates of (0.4361, 0.4992). Solid-state UV/Vis diffuse reflectance spectra reveal that it possesses wide optical band gap of 4.94 eV.
By means of solvothermal reactions, a novel lanthanide-mercury compound, {[Ho(IA)3(H3O)2]2n[2n(HgCl4)][n(HgCl5)]}·3nH3O·nH2O (1, HIA = isonicotinc acid) was prepared and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system with a = 24.2147(5), b = 20.8106(4), c = 15.3060(3) Å, β = 128.326(2)°, V = 6050.8(2) Å3, C36H45Cl13Hg3Ho2N6O20, Mr = 2274.26, Z = 4, Dc = 2.497 g/cm3, μ(MoKα) = 10.817 mm–1 and F(000) = 4232. It exhibits a one-dimensional (1-D) chain-like structure. Solid-state photoluminescence measurement shows that it displays brown light emission bands. These emission bands originate from the characteristic emissions of the 4f electrons intrashell transitions of 5S2 → 5I8 and 5F5 → 5I8 of the holmium(Ⅲ) ions in 1. The photoluminescence emission energy transfer mechanism is elucidated by the energy level diagrams of the holmium(Ⅲ) ions and isonicotinic acid ligand. Complex 1 has CIE chromaticity coordinates of (0.4361, 0.4992). Solid-state UV/Vis diffuse reflectance spectra reveal that it possesses wide optical band gap of 4.94 eV.
2020, 39(4): 756-764
doi: 10.14102/j.cnki.0254-5861.2011-2496
Abstract:
Layered sodium manganese oxides (LSMOs), with two-dimensional channels for ion diffusion, have been regarded as the promising electrode materials in the application of asymmetric supercapacitors (ASCs). In this work, the layered Na0.5Mn2O4·1.5H2O was synthesized through a facile hydrothermal method by controlling the molar ratio of sodium and manganese. When the molar ratio of sodium to manganese is 3:1, Na0.5Mn2O4·1.5H2O has shown the best capacitance of 369 F/g with current density of 0.5 A/g, and maintained a capacitance of 265 F/g after 2000 cycles. The asymmetric supercapacitor consists of the sodium manages oxides as the positive electrode and active carbon (AC) as the negative electrode in 1 mol/L Na2SO4 solution. The voltage of the asymmetric supercapacitor has been expanded to 0~2 V with an energy density of 10.13 Wh/kg at a power density of 500 W/kg based on the total weight of both active electrode materials when the mass ratio of AC to Na0.5Mn2O4·1.5H2O was 3:1.
Layered sodium manganese oxides (LSMOs), with two-dimensional channels for ion diffusion, have been regarded as the promising electrode materials in the application of asymmetric supercapacitors (ASCs). In this work, the layered Na0.5Mn2O4·1.5H2O was synthesized through a facile hydrothermal method by controlling the molar ratio of sodium and manganese. When the molar ratio of sodium to manganese is 3:1, Na0.5Mn2O4·1.5H2O has shown the best capacitance of 369 F/g with current density of 0.5 A/g, and maintained a capacitance of 265 F/g after 2000 cycles. The asymmetric supercapacitor consists of the sodium manages oxides as the positive electrode and active carbon (AC) as the negative electrode in 1 mol/L Na2SO4 solution. The voltage of the asymmetric supercapacitor has been expanded to 0~2 V with an energy density of 10.13 Wh/kg at a power density of 500 W/kg based on the total weight of both active electrode materials when the mass ratio of AC to Na0.5Mn2O4·1.5H2O was 3:1.
2020, 39(4): 765-771
doi: 10.14102/j.cnki.0254-5861.2011-2489
Abstract:
A new complex [Mn(DHTA)(bipy)0.5]n (1, H2DHTA = 2,5-dihydroxy-1,4-benzene-dicarboxylic acid, bipy = 2,2΄-bipyridine) was hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, single-crystal and power X-ray diffraction. It belongs to monoclinic system, C2/c space group with a = 12.874(13), b = 11.302(12), c = 17.352(18) Å, β = 101.574(15)°, V = 2474(4) Å3 and Z = 4. It displays a one-dimensional zigzag chain-like structure, which was further extended into a three-dimensional supramolecular structure by hydrogen bonds and π-π interactions. Moreover, we analyzed Natural Bond Orbital (NBO) of 1 in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results show the obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ion.
A new complex [Mn(DHTA)(bipy)0.5]n (1, H2DHTA = 2,5-dihydroxy-1,4-benzene-dicarboxylic acid, bipy = 2,2΄-bipyridine) was hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, single-crystal and power X-ray diffraction. It belongs to monoclinic system, C2/c space group with a = 12.874(13), b = 11.302(12), c = 17.352(18) Å, β = 101.574(15)°, V = 2474(4) Å3 and Z = 4. It displays a one-dimensional zigzag chain-like structure, which was further extended into a three-dimensional supramolecular structure by hydrogen bonds and π-π interactions. Moreover, we analyzed Natural Bond Orbital (NBO) of 1 in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results show the obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ion.
2020, 39(4): 772-782
doi: 10.14102/j.cnki.0254-5861.2011-2562
Abstract:
Based on the solvothermal reaction of 5,5΄-(1,3,6,8-tetraoxobenzo[lmn][3,8] phenanthrolin-2-7-diyl)bis-1,3-benzenedicarboxylic acid (H4L) linker and Zn(Ⅱ)/Cd(Ⅱ), two new 2D coordination polymers (CPs), namely {[ZnH2L(4,4΄-bibp)]·H2O}n (1) and {[CdL0.5(1,4-bimb)0.5(H2O)]·EtOH}n (2) (L = BIPA-TC), have been successfully constructed and characterized by EA, PXRD and IR with the aid of 4,4΄-bis(benzoimidazo-1-yl)biphenyl(4,4΄-bbib)/1,4-bis(imidazol-1-ylmethyl)benzene (1,4-bimb). The structural analysis showed that complex 1 exhibits a 3D supramolecular structure with the topology of sql, and complex 2 possesses a 2-nodal (4,6)-c framework with the topology of (32·42·52)(34·44·54·63)-4,6T26. Fluorescent experiments showed that 1 and 2 have high selectivity and sensitivity for the sensing of nitroaromatic compounds and Fe3+ in aqueous solutions.
Based on the solvothermal reaction of 5,5΄-(1,3,6,8-tetraoxobenzo[lmn][3,8] phenanthrolin-2-7-diyl)bis-1,3-benzenedicarboxylic acid (H4L) linker and Zn(Ⅱ)/Cd(Ⅱ), two new 2D coordination polymers (CPs), namely {[ZnH2L(4,4΄-bibp)]·H2O}n (1) and {[CdL0.5(1,4-bimb)0.5(H2O)]·EtOH}n (2) (L = BIPA-TC), have been successfully constructed and characterized by EA, PXRD and IR with the aid of 4,4΄-bis(benzoimidazo-1-yl)biphenyl(4,4΄-bbib)/1,4-bis(imidazol-1-ylmethyl)benzene (1,4-bimb). The structural analysis showed that complex 1 exhibits a 3D supramolecular structure with the topology of sql, and complex 2 possesses a 2-nodal (4,6)-c framework with the topology of (32·42·52)(34·44·54·63)-4,6T26. Fluorescent experiments showed that 1 and 2 have high selectivity and sensitivity for the sensing of nitroaromatic compounds and Fe3+ in aqueous solutions.
Synthesis and Characterization of a Terpyridine Ligand and Its Interactions with Selected Metal Ions
2020, 39(4): 783-792
doi: 10.14102/j.cnki.0254-5861.2011-2498
Abstract:
In this work, a terpyridine ligand L, (4΄-phenyl-2,2΄:6΄,2΄΄-terpyridine), was synthesized and fully characterized. Interactions of the ligand with selected metal ions like Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ) were investigated. Compared to ligand L, only Fe(Ⅱ) and Pb(Ⅱ) ions show new band in electronic absorption spectroscopy. Fluorescent spectroscopy indicates that Zn(Ⅱ) and Cd(Ⅱ) ions enhance the emission intensity of ligand L, and other selected ions quench emission intensity. To explore how Fe(Ⅱ) ion interacts with ligand L, Fe(L)-based complex 1 was synthesized, spectroscopic studies and single-crystal X-ray diffraction analysis. This implies ligand L has an excellent selectivity for Zn(Ⅱ) and Cd(Ⅱ) ions.
In this work, a terpyridine ligand L, (4΄-phenyl-2,2΄:6΄,2΄΄-terpyridine), was synthesized and fully characterized. Interactions of the ligand with selected metal ions like Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ) were investigated. Compared to ligand L, only Fe(Ⅱ) and Pb(Ⅱ) ions show new band in electronic absorption spectroscopy. Fluorescent spectroscopy indicates that Zn(Ⅱ) and Cd(Ⅱ) ions enhance the emission intensity of ligand L, and other selected ions quench emission intensity. To explore how Fe(Ⅱ) ion interacts with ligand L, Fe(L)-based complex 1 was synthesized, spectroscopic studies and single-crystal X-ray diffraction analysis. This implies ligand L has an excellent selectivity for Zn(Ⅱ) and Cd(Ⅱ) ions.
2020, 39(4): 793-800
doi: 10.14102/j.cnki.0254-5861.2011-2393
Abstract:
Three new lanthanide coordination polymers [Ln(bppc)2(suc)0.5(H2O)]n·nH2O (Ln = Eu(1), Ln = Dy(2), Ln = Tb(3), Hbppc = 2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate, H2suc = succinic acid) have been hydrothermally synthesized and structurally characterized. These compounds are isostructural and crystallize in triclinic\begin{document}$ P\overline 1 $\end{document}
Three new lanthanide coordination polymers [Ln(bppc)2(suc)0.5(H2O)]n·nH2O (Ln = Eu(1), Ln = Dy(2), Ln = Tb(3), Hbppc = 2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate, H2suc = succinic acid) have been hydrothermally synthesized and structurally characterized. These compounds are isostructural and crystallize in triclinic
2020, 39(4): 801-808
doi: 10.14102/j.cnki.0254-5861.2011-2500
Abstract:
Two protic pyrazolium ionic liquids (ILs) are synthesized and characterized by mass spectra (MS), 1H NMR, 13C NMR, and single-crystal X-ray diffraction. Then, their catalytic activity for the cycloaddition of PO and CO2 is investigated. Two protic pyrazolium ILs are the orthorhombic and triclinic systems of space groups Cmca and C2/c for HTMPzBr and HDMPzBr, respectively. They could catalyze the cycloaddition reaction of carbon dioxide (CO2) with epoxides (PO) to produce cyclic carbonate (PC) without any solvent and co-catalyst and show strong catalytic activity when the reaction temperature is over 110 ℃.
Two protic pyrazolium ionic liquids (ILs) are synthesized and characterized by mass spectra (MS), 1H NMR, 13C NMR, and single-crystal X-ray diffraction. Then, their catalytic activity for the cycloaddition of PO and CO2 is investigated. Two protic pyrazolium ILs are the orthorhombic and triclinic systems of space groups Cmca and C2/c for HTMPzBr and HDMPzBr, respectively. They could catalyze the cycloaddition reaction of carbon dioxide (CO2) with epoxides (PO) to produce cyclic carbonate (PC) without any solvent and co-catalyst and show strong catalytic activity when the reaction temperature is over 110 ℃.
