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2020 Volume 39 Issue 5
2020, 39(5): 815-820
doi: 10.14102/j.cnki.0254–5861.2011–2830
Abstract:
The layered 122 Zintl compounds have become an intriguing class of thermoelectric materials due to the promising electronic transport properties and inherently low thermal conductivity, showing the typical characteristics of "phonon-glass electron-crystal". Owing to the unprecedented performance tunability, the thermoelectric properties of the layered-structure compounds are completive with some traditional thermoelectric materials. Point defects involving vacancy, aliovalent doping and equivalent alloying atoms have been introduced to further enhance the thermoelectric properties. This review emphasizes the effects of various point defects on the thermoelectric parameters, and provides perspective on the strategies for increasing the thermoelectric figure of merit zT, which are believed to be applicable for improving the thermoelectric properties of many other compounds.
The layered 122 Zintl compounds have become an intriguing class of thermoelectric materials due to the promising electronic transport properties and inherently low thermal conductivity, showing the typical characteristics of "phonon-glass electron-crystal". Owing to the unprecedented performance tunability, the thermoelectric properties of the layered-structure compounds are completive with some traditional thermoelectric materials. Point defects involving vacancy, aliovalent doping and equivalent alloying atoms have been introduced to further enhance the thermoelectric properties. This review emphasizes the effects of various point defects on the thermoelectric parameters, and provides perspective on the strategies for increasing the thermoelectric figure of merit zT, which are believed to be applicable for improving the thermoelectric properties of many other compounds.
2020, 39(5): 821-830
doi: 10.14102/j.cnki.0254–5861.2011–2850
Abstract:
The widespread applications of thermoelectric (TE) materials in power generation and solid-state cooling require improving their TE figure of merit (ZT) significantly. Recently, GeTe-based alloys have shown great promise as mid-temperature TE materials with superhigh TE performance, mostly due to their relatively high-degeneracy band structures and low lattice thermal conductivity. In this perspective, we review the most recent progress of the GeTe-based TE alloys from the view of phase and defect engineering. These two strategies are the most widely-used and efficient approaches in GeTe-based alloys to optimize the transport properties of electrons and phonons for high ZT. The phase transition from rhombohedral to cubic structure is believed to improve the band convergence of GeTe-based alloys for higher electrical performance. Typical defects in GeTe-based alloys include the point defects from Ge vacancies and substitutional dopants, linear and planar defects from Ge vacancies. The defect engineering of GeTe-based alloys is important not only for optimizing the carrier density but also for tuning the band structure and phonon-scattering processes. The summarized strategies in this review can also be used as a reference for guiding the further development of GeTe-based alloys and also other TE materials.
The widespread applications of thermoelectric (TE) materials in power generation and solid-state cooling require improving their TE figure of merit (ZT) significantly. Recently, GeTe-based alloys have shown great promise as mid-temperature TE materials with superhigh TE performance, mostly due to their relatively high-degeneracy band structures and low lattice thermal conductivity. In this perspective, we review the most recent progress of the GeTe-based TE alloys from the view of phase and defect engineering. These two strategies are the most widely-used and efficient approaches in GeTe-based alloys to optimize the transport properties of electrons and phonons for high ZT. The phase transition from rhombohedral to cubic structure is believed to improve the band convergence of GeTe-based alloys for higher electrical performance. Typical defects in GeTe-based alloys include the point defects from Ge vacancies and substitutional dopants, linear and planar defects from Ge vacancies. The defect engineering of GeTe-based alloys is important not only for optimizing the carrier density but also for tuning the band structure and phonon-scattering processes. The summarized strategies in this review can also be used as a reference for guiding the further development of GeTe-based alloys and also other TE materials.
2020, 39(5): 831-837
doi: 10.14102/j.cnki.0254–5861.2011–2867
Abstract:
Thermoelectric materials can directly achieve the conversion between heat and electricity, providing a clean and reliable way to alleviate energy crisis. However, the wide use of thermoelectric materials is subjected to their low energy conversion efficiency. Grain boundary engineering is considered as an effective strategy to improve thermoelectric performance, particularly for the most polycrystalline thermoelectric materials in bulk state. Recently, the precise controlling over the microstructure and composition of grain boundary at atomic scale has been achieved by atomic layer deposition (ALD) technology, which has been confirmed in various thermoelectric materials, such as Bi2Te2.7Se0.3, Bi0.4Sb1.6Te3, and ZrNiSn. Importantly, it is demonstrated that the decoupling between three key thermoelectric parameters, i.e. Seebeck coefficient, electrical conductivity and thermal conductivity, can be realized by ALD-based grain boundary engineering. Moreover, these key parameters can be optimized simultaneously toward the desired direction, which is extremely important for improving the thermoelectric performance. In this review, the relevant progress on the grain boundary engineering by ALD-based strategy is reviewed and some prospects are proposed.
Thermoelectric materials can directly achieve the conversion between heat and electricity, providing a clean and reliable way to alleviate energy crisis. However, the wide use of thermoelectric materials is subjected to their low energy conversion efficiency. Grain boundary engineering is considered as an effective strategy to improve thermoelectric performance, particularly for the most polycrystalline thermoelectric materials in bulk state. Recently, the precise controlling over the microstructure and composition of grain boundary at atomic scale has been achieved by atomic layer deposition (ALD) technology, which has been confirmed in various thermoelectric materials, such as Bi2Te2.7Se0.3, Bi0.4Sb1.6Te3, and ZrNiSn. Importantly, it is demonstrated that the decoupling between three key thermoelectric parameters, i.e. Seebeck coefficient, electrical conductivity and thermal conductivity, can be realized by ALD-based grain boundary engineering. Moreover, these key parameters can be optimized simultaneously toward the desired direction, which is extremely important for improving the thermoelectric performance. In this review, the relevant progress on the grain boundary engineering by ALD-based strategy is reviewed and some prospects are proposed.
2020, 39(5): 838-848
doi: 10.14102/j.cnki.0254–5861.2011–2510
Abstract:
Using B3LYP and M06-2X functionals, eight noncovalent configurations for the adsorption of D-penicillamine drug (DPA) drug on poly(amidoamine) G0 generation dendrimer (PAMAMG0) carrier have been investigated. The quantum molecular descriptors and the binding and solvation energies were examined in aqueous solution and gas phase. The binding energies demonstrated the energetic stability of non-bonded species (PAMAMG0/DPA1-8). The solvation energies showed that solubility of DPA rises in the vicinity of PAMAMG0 carrier which is a fundamental factor for applicability of a carrier. Considering quantum molecular descriptors such as electrophilicity power and global hardness, the toxicity of DPA drug in the vicinity of PAMAMG0 carrier decreases and drug release is facilitated. The AIM analysis for all PAMAMG0/DPA1-8 structures indicated that the hydrogen and pseudo-hydrogen bonds play important roles in the functionalization of PAMAMG0 with DPA drug. The configuration in which DPA drug interacts simultaneously with two -NH2 functional groups of PAMAMG0 is the most stable configuration.
Using B3LYP and M06-2X functionals, eight noncovalent configurations for the adsorption of D-penicillamine drug (DPA) drug on poly(amidoamine) G0 generation dendrimer (PAMAMG0) carrier have been investigated. The quantum molecular descriptors and the binding and solvation energies were examined in aqueous solution and gas phase. The binding energies demonstrated the energetic stability of non-bonded species (PAMAMG0/DPA1-8). The solvation energies showed that solubility of DPA rises in the vicinity of PAMAMG0 carrier which is a fundamental factor for applicability of a carrier. Considering quantum molecular descriptors such as electrophilicity power and global hardness, the toxicity of DPA drug in the vicinity of PAMAMG0 carrier decreases and drug release is facilitated. The AIM analysis for all PAMAMG0/DPA1-8 structures indicated that the hydrogen and pseudo-hydrogen bonds play important roles in the functionalization of PAMAMG0 with DPA drug. The configuration in which DPA drug interacts simultaneously with two -NH2 functional groups of PAMAMG0 is the most stable configuration.
2020, 39(5): 849-854
doi: 10.14102/j.cnki.0254–5861.2011–2531
Abstract:
A series of derivatives of pyridazine were designed through substituting hydrogens on the pyridazine ring with nitro groups. To explore the thermal stability of the title molecules, heats of formation, bond dissociation energies, and bond orders were calculated at the B3PW91/6-311+G(d, p) level. To confirm the potential usage as high energy density compounds, the detonation pressure and detonation velocity were predicted by using the empirical Kamlet-Jacobs (K-J) equation. Based on our calculated results, both thermal and kinetic stabilities of the title molecules are confirmed with good detonation characters. Especially, 3, 4, 5-trinitropyridazide and 3, 4, 6-trinitropyridazide represent excellent detonation parameters better than 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane (RDX) and are screened out as potential high energy density compounds.
A series of derivatives of pyridazine were designed through substituting hydrogens on the pyridazine ring with nitro groups. To explore the thermal stability of the title molecules, heats of formation, bond dissociation energies, and bond orders were calculated at the B3PW91/6-311+G(d, p) level. To confirm the potential usage as high energy density compounds, the detonation pressure and detonation velocity were predicted by using the empirical Kamlet-Jacobs (K-J) equation. Based on our calculated results, both thermal and kinetic stabilities of the title molecules are confirmed with good detonation characters. Especially, 3, 4, 5-trinitropyridazide and 3, 4, 6-trinitropyridazide represent excellent detonation parameters better than 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane (RDX) and are screened out as potential high energy density compounds.
2020, 39(5): 855-860
doi: 10.14102/j.cnki.0254–5861.2011–2534
Abstract:
A 3D-QSAR study was conducted to analyze the anti-tumor activity (pHs, s = 1, 6) of dihydropyridin-2-one containing histone deacetylase inhibitor (DHDACi) to histone deacetylase (HDACs, s = 1, 6) by the comparative molecular field analysis (CoMFA) method. The predicting model was established based on the training set of 22 compounds, which was verified by the test set of 6 compounds containing template molecule. The results showed that the contributions of steric and electrostatic fields to pH1 are 37.6% and 62.4%, and those to pH6 are 44.6% and 55.4%, respectively. The coefficients of the cross-validation (Rcv2) and the non cross-validation (R2) are 0.574 and 0.947 for pH1, and 0.488 and 0.884 for pH6, respectively. The models were then used to predict the activities of the compounds for the training and testing sets. The results indicated that the models had strong stability and good predictability. Based on the 3D contour maps, several new potential inhibitors with higher anti-tumor activity were designed. However, the effectiveness of these potential inhibitors is still needed to be verified by the experimental results.
A 3D-QSAR study was conducted to analyze the anti-tumor activity (pHs, s = 1, 6) of dihydropyridin-2-one containing histone deacetylase inhibitor (DHDACi) to histone deacetylase (HDACs, s = 1, 6) by the comparative molecular field analysis (CoMFA) method. The predicting model was established based on the training set of 22 compounds, which was verified by the test set of 6 compounds containing template molecule. The results showed that the contributions of steric and electrostatic fields to pH1 are 37.6% and 62.4%, and those to pH6 are 44.6% and 55.4%, respectively. The coefficients of the cross-validation (Rcv2) and the non cross-validation (R2) are 0.574 and 0.947 for pH1, and 0.488 and 0.884 for pH6, respectively. The models were then used to predict the activities of the compounds for the training and testing sets. The results indicated that the models had strong stability and good predictability. Based on the 3D contour maps, several new potential inhibitors with higher anti-tumor activity were designed. However, the effectiveness of these potential inhibitors is still needed to be verified by the experimental results.
2020, 39(5): 861-872
doi: 10.14102/j.cnki.0254–5861.2011–2485
Abstract:
We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations. The geometries and energetic values of all stationaries and transition states involved in the three different reaction pathways (Channels I, Ⅱ and Ⅲ) are reported and analyzed. All reaction mechanisms are fully different from that of MoxOy catalyzing volatile organic compounds (VOCs) in previous studies. The completely new mechanisms catalyzed by MoO2 for acetic acid have been discovered for the first time. Channels I (IA and IB) and Ⅱ are both addition reactions and channel Ⅲ is hydrogen abstraction reaction by producing a leaving group. The barrier energies of reaction are also compared with other catalytic reactions, showing that MoO2 catalyst expresses a lower barrier energy (8.22 kcal/mol) by addition reaction, which represents MoO2 tends to absorb acetic acid pollution gas via addition reaction rather than release toxic substances. This also means that MoO2 is a more effective and representative catalyst and is suitable for further study of catalytic carboxylic acids, so the reaction mechanisms may provide a useful theoretical guidance and solution for the catalysis of carboxylic acids.
We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations. The geometries and energetic values of all stationaries and transition states involved in the three different reaction pathways (Channels I, Ⅱ and Ⅲ) are reported and analyzed. All reaction mechanisms are fully different from that of MoxOy catalyzing volatile organic compounds (VOCs) in previous studies. The completely new mechanisms catalyzed by MoO2 for acetic acid have been discovered for the first time. Channels I (IA and IB) and Ⅱ are both addition reactions and channel Ⅲ is hydrogen abstraction reaction by producing a leaving group. The barrier energies of reaction are also compared with other catalytic reactions, showing that MoO2 catalyst expresses a lower barrier energy (8.22 kcal/mol) by addition reaction, which represents MoO2 tends to absorb acetic acid pollution gas via addition reaction rather than release toxic substances. This also means that MoO2 is a more effective and representative catalyst and is suitable for further study of catalytic carboxylic acids, so the reaction mechanisms may provide a useful theoretical guidance and solution for the catalysis of carboxylic acids.
2020, 39(5): 873-883
doi: 10.14102/j.cnki.0254–5861.2011–2507
Abstract:
Food waste orange peel was employed as a raw material to prepare biomass adsorbent to solve the indoor Total Volatile Organic Compounds (TVOC). The preparation process of orange peel treated with KOH was optimized by the quadratic regression orthogonal rotation, and the regression model and optimal processing conditions were obtained. The structure of the adsorbent was characterized by BET, SEM, TEM, EDS, XRD and FTIR analysis. The adsorption properties and desorption regeneration were discussed. The results showed the maximal removal rate Ymax was 9.4824% when KOH concentration was 0.3 mol/L, the soaking time of KOH was 26 h and that of HCl was 2.89 h. The best single factor condition was the adsorbent with 40 mesh size and 6.0 g. The adsorption of modified orange peel on TVOC conformed to the Freundlich models, which was more inclined to multi-layer active site adsorption. The adsorption law followed the quasi-second-order kinetic model (R2 = 0.955), indicating the adsorption was a physico-chemical mixture but controlled by physical adsorption and it was a spontaneous endothermic process. The modified orange peel exposed more sites and had stronger chemical groups, which were beneficial to adsorption. The adsorbent has a significantly better TVOC removal rate than other materials at 1% level, that is, modified orange peel > diatomite > activated carbon > bamboo charcoal > macroporous resin. In addition, it had good recycling and regeneration capacity.
Food waste orange peel was employed as a raw material to prepare biomass adsorbent to solve the indoor Total Volatile Organic Compounds (TVOC). The preparation process of orange peel treated with KOH was optimized by the quadratic regression orthogonal rotation, and the regression model and optimal processing conditions were obtained. The structure of the adsorbent was characterized by BET, SEM, TEM, EDS, XRD and FTIR analysis. The adsorption properties and desorption regeneration were discussed. The results showed the maximal removal rate Ymax was 9.4824% when KOH concentration was 0.3 mol/L, the soaking time of KOH was 26 h and that of HCl was 2.89 h. The best single factor condition was the adsorbent with 40 mesh size and 6.0 g. The adsorption of modified orange peel on TVOC conformed to the Freundlich models, which was more inclined to multi-layer active site adsorption. The adsorption law followed the quasi-second-order kinetic model (R2 = 0.955), indicating the adsorption was a physico-chemical mixture but controlled by physical adsorption and it was a spontaneous endothermic process. The modified orange peel exposed more sites and had stronger chemical groups, which were beneficial to adsorption. The adsorbent has a significantly better TVOC removal rate than other materials at 1% level, that is, modified orange peel > diatomite > activated carbon > bamboo charcoal > macroporous resin. In addition, it had good recycling and regeneration capacity.
2020, 39(5): 884-888
doi: 10.14102/j.cnki.0254–5861.2011–2516
Abstract:
A block-like metal-organic framework UiO-66 was prepared by in-situ growth one-pot hydrothermal process. The as-synthesized material was characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The electrochemical properties used as a supercapacitor electrode material were evaluated by cyclic voltammetry (CV), galvanostatic charge-discharge measurement (GCD) and electrochemical impedance spectroscopy (EIS) in 2 M KOH solution, exhibiting a high specific capacitance (311 F·g-1 at 1 A·g-1), suggesting its promising potential as a supercapacitor electrode material.
A block-like metal-organic framework UiO-66 was prepared by in-situ growth one-pot hydrothermal process. The as-synthesized material was characterized by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The electrochemical properties used as a supercapacitor electrode material were evaluated by cyclic voltammetry (CV), galvanostatic charge-discharge measurement (GCD) and electrochemical impedance spectroscopy (EIS) in 2 M KOH solution, exhibiting a high specific capacitance (311 F·g-1 at 1 A·g-1), suggesting its promising potential as a supercapacitor electrode material.
2020, 39(5): 889-894
doi: 10.14102/j.cnki.0254-5861.2011-2517
Abstract:
A novel organic-inorganic hybrid phase transition compound [(C3H7)2dabco]CoBr4 with switchable dielectric property is synthesized, and the phase transition behavior was measured by DSC measurements. The DSC curves display a pair of endothermic and exothermic peaks at 230 and 212 K, confirming a reversible first-order phase transition by the calculation of entropy change and the 18 K thermal hysteresis. The structural change from P42/m at room-temperature to P42 at 100 K accompanied by a deletion of mirror plane m was determined by variable temperature single-crystal X-ray diffractions. Furthermore, switchable step-like dielectric anomalies can be observed around 230 K by the real part of dielectric constant curves. The 10-fold difference of ε' between high ε' and low ε' states make compound 1 a potential candidate for sensor and detection devices at appropriate temperature and frequencies.
A novel organic-inorganic hybrid phase transition compound [(C3H7)2dabco]CoBr4 with switchable dielectric property is synthesized, and the phase transition behavior was measured by DSC measurements. The DSC curves display a pair of endothermic and exothermic peaks at 230 and 212 K, confirming a reversible first-order phase transition by the calculation of entropy change and the 18 K thermal hysteresis. The structural change from P42/m at room-temperature to P42 at 100 K accompanied by a deletion of mirror plane m was determined by variable temperature single-crystal X-ray diffractions. Furthermore, switchable step-like dielectric anomalies can be observed around 230 K by the real part of dielectric constant curves. The 10-fold difference of ε' between high ε' and low ε' states make compound 1 a potential candidate for sensor and detection devices at appropriate temperature and frequencies.
2020, 39(5): 895-900
doi: 10.14102/j.cnki.0254-5861.2011-2585
Abstract:
We have synthesized one novel Schiff-base ligand by modifying the aromatic aldehyde: H2L1 (H2L1 = N, N'-bis(2-oxy-acetate-3-methoxyl)benzylpropylene-ethanediamine). [Co(Ⅱ)L1]2·2EtOH (1) was prepared by the reaction between H2L1 and CoCl2·6H2O in the solvent of C2H5OH. The title compound was structurally characterized by elemental analysis, IR, H NMR and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.472(3), b = 13.4842(13), c = 15.1848(15) Å, β = 115.626(1)°, V = 5441.0(9) Å3, C28H22CoN2O8.50, Mr = 581.41, Dc = 1.420 g/cm3, μ(MoKα) = 0.685 mm-1, F(000) = 2392, Z = 8, the final R = 0.0541 and wR = 0.1565 (I > 2σ(I)). The Co(Ⅱ) atom is hexa-coordinated, furnishing a triangular prism geometry. It is interesting that the H-bond intersections formed a one-dimensional chain structure. In this paper, we research the synthesis, characterization, oxygen respiratory, antibacterial activity, and photoluminescent property of complex 1.
We have synthesized one novel Schiff-base ligand by modifying the aromatic aldehyde: H2L1 (H2L1 = N, N'-bis(2-oxy-acetate-3-methoxyl)benzylpropylene-ethanediamine). [Co(Ⅱ)L1]2·2EtOH (1) was prepared by the reaction between H2L1 and CoCl2·6H2O in the solvent of C2H5OH. The title compound was structurally characterized by elemental analysis, IR, H NMR and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.472(3), b = 13.4842(13), c = 15.1848(15) Å, β = 115.626(1)°, V = 5441.0(9) Å3, C28H22CoN2O8.50, Mr = 581.41, Dc = 1.420 g/cm3, μ(MoKα) = 0.685 mm-1, F(000) = 2392, Z = 8, the final R = 0.0541 and wR = 0.1565 (I > 2σ(I)). The Co(Ⅱ) atom is hexa-coordinated, furnishing a triangular prism geometry. It is interesting that the H-bond intersections formed a one-dimensional chain structure. In this paper, we research the synthesis, characterization, oxygen respiratory, antibacterial activity, and photoluminescent property of complex 1.
2020, 39(5): 901-907
doi: 10.14102/j.cnki.0254–5861.2011–2542
Abstract:
Two new isochroman derivatives (1 and 2) were isolated from the fermentation products of mangrove endophytic fungus Phomopsis sp. 33#. Their structures were characterized by IR, 1H NMR, H RMS, and single-crystal X-ray crystallography. The anticancer activity of the two compounds was investigated against four human lung cancer cells (NCI-H292, NCI-H460, LTEP-A-2 and MSTO-211) by 3-(4, 5)-dimethylthiahiazo(-z-y1)-3, 5-di-phenytetrazoliumromide (MTT) assay. Furthermore, molecular docking studies supported the biological assay data, showing that compared with 1, compound 2 has stronger interaction with protein.
Two new isochroman derivatives (1 and 2) were isolated from the fermentation products of mangrove endophytic fungus Phomopsis sp. 33#. Their structures were characterized by IR, 1H NMR, H RMS, and single-crystal X-ray crystallography. The anticancer activity of the two compounds was investigated against four human lung cancer cells (NCI-H292, NCI-H460, LTEP-A-2 and MSTO-211) by 3-(4, 5)-dimethylthiahiazo(-z-y1)-3, 5-di-phenytetrazoliumromide (MTT) assay. Furthermore, molecular docking studies supported the biological assay data, showing that compared with 1, compound 2 has stronger interaction with protein.
2020, 39(5): 908-912
doi: 10.14102/j.cnki.0254-5861.2011-2597
Abstract:
The target compound (C18H14O4) was synthesized and structurally determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/n with a = 7.9383(6), b = 19.5083(13), c = 9.4189(7) Å, β = 98.981(2)°, C18H14O4, Mr = 294.29, Dc = 1.357 g/cm3, V = 1440.75(18) Å3, Z = 4, F(000) = 616, µ(MoKa) = 0.096 mm-1, T = 293(2) K, 3320 independent reflections with 1845 observed ones (I > 2σ(I)), R = 0.0529 and wR = 0.1082 with GOF = 1.015 (R = 0.1202 and wR = 0.1278 for all data). The phenanthrene skeleton is coplanar. The overall crystal packing revealed that it has reverse staggered parallel and stratified arrangement. And a one-dimensional interaction model was formed by two kinds of π-π interactions between the two adjacent molecules at upper and lower levels. The decomposition mechanism of compound 3 is complex.
The target compound (C18H14O4) was synthesized and structurally determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/n with a = 7.9383(6), b = 19.5083(13), c = 9.4189(7) Å, β = 98.981(2)°, C18H14O4, Mr = 294.29, Dc = 1.357 g/cm3, V = 1440.75(18) Å3, Z = 4, F(000) = 616, µ(MoKa) = 0.096 mm-1, T = 293(2) K, 3320 independent reflections with 1845 observed ones (I > 2σ(I)), R = 0.0529 and wR = 0.1082 with GOF = 1.015 (R = 0.1202 and wR = 0.1278 for all data). The phenanthrene skeleton is coplanar. The overall crystal packing revealed that it has reverse staggered parallel and stratified arrangement. And a one-dimensional interaction model was formed by two kinds of π-π interactions between the two adjacent molecules at upper and lower levels. The decomposition mechanism of compound 3 is complex.
2020, 39(5): 913-917
doi: 10.14102/j.cnki.0254-5861.2011-2565
Abstract:
The target compound (C19H20ClNO) was structurally determined by single-crystal X-ray diffraction. The crystal is in monoclinic system, space group P21/n with a = 9.2365(2), b = 12.1241(3), c = 14.9960(4) Å, β = 106.589(3)°, C19H20ClNO, Mr = 313.81, Dc = 1.295 g/cm3, V = 1609.42(7) Å3, Z = 4, F(000) = 664, µ(MoKa) = 2.097 mm-1, T = 200(10) K, 2813 independent reflections with 2533 observed ones (I > 2σ(I)), R = 0.0389 and wR = 0.1057 with GOF = 1.043 (R = 0.0423 and wR = 0.1083 for all data). The 3, 4-dihydroquinolin-2(1H)-one moiety maintains thermodynamically stable trans configuration. The decomposition mechanism of compound 3 is complex by thermal analysis.
The target compound (C19H20ClNO) was structurally determined by single-crystal X-ray diffraction. The crystal is in monoclinic system, space group P21/n with a = 9.2365(2), b = 12.1241(3), c = 14.9960(4) Å, β = 106.589(3)°, C19H20ClNO, Mr = 313.81, Dc = 1.295 g/cm3, V = 1609.42(7) Å3, Z = 4, F(000) = 664, µ(MoKa) = 2.097 mm-1, T = 200(10) K, 2813 independent reflections with 2533 observed ones (I > 2σ(I)), R = 0.0389 and wR = 0.1057 with GOF = 1.043 (R = 0.0423 and wR = 0.1083 for all data). The 3, 4-dihydroquinolin-2(1H)-one moiety maintains thermodynamically stable trans configuration. The decomposition mechanism of compound 3 is complex by thermal analysis.
2020, 39(5): 918-926
doi: 10.14102/j.cnki.0254-5861.2011-2595
Abstract:
A new dinuclear copper(Ⅱ) compound [Cu2(CH3COO)2(L)2(H2O)2]·4H2O (1, HL = 4-pyridyl-NH-1, 2, 3-triazole) has been synthesized and characterized. Single-crystal X-ray diffraction showed that complex 1 crystallizes in monoclinic space group P21/c with a = 0.8427(1), b = 1.0981(1), c = 1.3610(1) nm, β = 93.364(4)°, V = 1.2573(1) nm3, Mr = 643.56, Z = 2, Dc = 1.700 g/cm3, μ = 1.760 mm-1, R = 0.0376, wR = 0.0981, and possesses a planar Cu2N4 six-membered ring, in which both Cu(Ⅱ) ions are bridged by two 1, 2, 3-triazole ligands. The neighboring dinuclear molecules are bound by strong intermolecular hydrogen bonds to create 1-D chains expanding along the b axis, which further form a 3-D supramolecular framework. Magnetic susceptibility measurement indicated the presence of weak antiferromagnetic interactions within the complex. The best fit using spin Hamiltonian yields the magnetic coupling constant J = –14.82 cm-1 above 30 K. The magnetic data are compared to those obtained for related double diazine bridged dinuclear copper(Ⅱ) complexes and magneto-structural correlations are discussed.
A new dinuclear copper(Ⅱ) compound [Cu2(CH3COO)2(L)2(H2O)2]·4H2O (1, HL = 4-pyridyl-NH-1, 2, 3-triazole) has been synthesized and characterized. Single-crystal X-ray diffraction showed that complex 1 crystallizes in monoclinic space group P21/c with a = 0.8427(1), b = 1.0981(1), c = 1.3610(1) nm, β = 93.364(4)°, V = 1.2573(1) nm3, Mr = 643.56, Z = 2, Dc = 1.700 g/cm3, μ = 1.760 mm-1, R = 0.0376, wR = 0.0981, and possesses a planar Cu2N4 six-membered ring, in which both Cu(Ⅱ) ions are bridged by two 1, 2, 3-triazole ligands. The neighboring dinuclear molecules are bound by strong intermolecular hydrogen bonds to create 1-D chains expanding along the b axis, which further form a 3-D supramolecular framework. Magnetic susceptibility measurement indicated the presence of weak antiferromagnetic interactions within the complex. The best fit using spin Hamiltonian yields the magnetic coupling constant J = –14.82 cm-1 above 30 K. The magnetic data are compared to those obtained for related double diazine bridged dinuclear copper(Ⅱ) complexes and magneto-structural correlations are discussed.
2020, 39(5): 927-932
doi: 10.14102/j.cnki.0254-5861.2011-2502
Abstract:
In this paper, a novel diiron ethane-1, 2-dithiolate complex [Fe2(CO)4{κ2-(Ph2P)2(1, 2-C6H4)}(μ-SCH2CH2S)] has been prepared and structurally characterized. Treatment of the parent complex [Fe2(CO)6(μ-SCH2CH2S)] with 1 equivalent of 1, 2-bis(diphenylphosphino)benzene and Me3NO∙2H2O as the oxidative agent gave the title complex in good yield. The title complex has been characterized by elemental analysis, IR, 1H NMR, 31P{1H} NMR, 13C{1H} NMR spectroscopy, and X-ray crystallography. X-ray crystal structure of the title complex contains a butterfly diiron cluster with a bridging ethane-1, 2-dithiolate, four terminal carbonyls, and a chelating 1, 2-bis(diphenylphosphino)benzene. In addition, electrochemical studies revealed that the title complex can catalyze the reduction of protons to H2 in the presence of acetic acid.
In this paper, a novel diiron ethane-1, 2-dithiolate complex [Fe2(CO)4{κ2-(Ph2P)2(1, 2-C6H4)}(μ-SCH2CH2S)] has been prepared and structurally characterized. Treatment of the parent complex [Fe2(CO)6(μ-SCH2CH2S)] with 1 equivalent of 1, 2-bis(diphenylphosphino)benzene and Me3NO∙2H2O as the oxidative agent gave the title complex in good yield. The title complex has been characterized by elemental analysis, IR, 1H NMR, 31P{1H} NMR, 13C{1H} NMR spectroscopy, and X-ray crystallography. X-ray crystal structure of the title complex contains a butterfly diiron cluster with a bridging ethane-1, 2-dithiolate, four terminal carbonyls, and a chelating 1, 2-bis(diphenylphosphino)benzene. In addition, electrochemical studies revealed that the title complex can catalyze the reduction of protons to H2 in the presence of acetic acid.
2020, 39(5): 933-941
doi: 10.14102/j.cnki.0254-5861.2011-2503
Abstract:
By adopting mixed-ligand strategy, two Co(Ⅱ) coordination polymers, [Co(phda)(itmb)(H2O)2]n (1) and [Co(phda)(Hpytz)]n (2) (H2phda = 1, 2-phenylenediacetate, itmb = 1-(imidazo-1-ly)-4-(1, 2, 4-triazol-1-yl methyl) benzene and Hpytz = 3, 5-di(4-pyridyl)-1, 2, 4-triazolate), were hydrothermally synthesized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The single-crystal X-ray diffraction reveals that two complexes feature carboxylato-bridged binuclear subunits extended further by the nitrogen-rich coligands to form different structures. Complex 1 containing phda-bridged binuclear cobalt is developed by itmb coligand to 1D double-stranded chain, whereas complex 2 exhibits 2D open bilayers, which result from the ribbon-like carboxylate chains pillared Hpytz coligands. In addition, the magnetic susceptibilities of both compounds were measured over the temperature range of 3~300 K, and the data were analyzed well using MagSaki software. The best fitting parameters were κ = 0.98, λ = −100 cm-1, ∆ = 588 cm-1 and J = 0.6 cm-1 for complex 1 and κ = 0.86, λ = −110 cm-1, ∆ = 756.8 cm-1 and J = −1.25 cm-1 for complex 2. The results indicate the existence of weaker ferromagnetic interaction for complex 1 and antiferromagnetic interaction for complex 2 between the metal centers in the dinuclear metal units.
By adopting mixed-ligand strategy, two Co(Ⅱ) coordination polymers, [Co(phda)(itmb)(H2O)2]n (1) and [Co(phda)(Hpytz)]n (2) (H2phda = 1, 2-phenylenediacetate, itmb = 1-(imidazo-1-ly)-4-(1, 2, 4-triazol-1-yl methyl) benzene and Hpytz = 3, 5-di(4-pyridyl)-1, 2, 4-triazolate), were hydrothermally synthesized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The single-crystal X-ray diffraction reveals that two complexes feature carboxylato-bridged binuclear subunits extended further by the nitrogen-rich coligands to form different structures. Complex 1 containing phda-bridged binuclear cobalt is developed by itmb coligand to 1D double-stranded chain, whereas complex 2 exhibits 2D open bilayers, which result from the ribbon-like carboxylate chains pillared Hpytz coligands. In addition, the magnetic susceptibilities of both compounds were measured over the temperature range of 3~300 K, and the data were analyzed well using MagSaki software. The best fitting parameters were κ = 0.98, λ = −100 cm-1, ∆ = 588 cm-1 and J = 0.6 cm-1 for complex 1 and κ = 0.86, λ = −110 cm-1, ∆ = 756.8 cm-1 and J = −1.25 cm-1 for complex 2. The results indicate the existence of weaker ferromagnetic interaction for complex 1 and antiferromagnetic interaction for complex 2 between the metal centers in the dinuclear metal units.
2020, 39(5): 942-948
doi: 10.14102/j.cnki.0254-5861.2011-2513
Abstract:
A novel heterometallic complex constructed by imidazole ligand, CoZn(C3N2H3)4 (1), has been synthesized under hydrothermal conditions. Compound 1 was characterized by IR spectra, thermal analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies reveals that compound 1 is in the tetragonal system, space group I41cd with a = 23.4371(5), b = 23.4371(5), c = 12.4430(7) Å, V = 6834.9(4) Å3, Z = 16, C12H12CoN8Zn, Mr = 392.60, Dc = 1.526 g/cm3, F(000) = 3152, μ = 2.381 mm-1, R = 0.0323 and wR = 0.0789. The CoZn(C3N2H3)4 is one-dimensional heterometallic molecular chains, which are further extended into a 3D open framework. Moreover, the solid-state fluorescence property of the complex has also been investigated at room temperature.
A novel heterometallic complex constructed by imidazole ligand, CoZn(C3N2H3)4 (1), has been synthesized under hydrothermal conditions. Compound 1 was characterized by IR spectra, thermal analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies reveals that compound 1 is in the tetragonal system, space group I41cd with a = 23.4371(5), b = 23.4371(5), c = 12.4430(7) Å, V = 6834.9(4) Å3, Z = 16, C12H12CoN8Zn, Mr = 392.60, Dc = 1.526 g/cm3, F(000) = 3152, μ = 2.381 mm-1, R = 0.0323 and wR = 0.0789. The CoZn(C3N2H3)4 is one-dimensional heterometallic molecular chains, which are further extended into a 3D open framework. Moreover, the solid-state fluorescence property of the complex has also been investigated at room temperature.
2020, 39(5): 949-954
doi: 10.14102/j.cnki.0254-5861.2011-2523
Abstract:
A novel tetranuclear copper cluster [Cu4(μ-L)6Cl2] was constructed by 2-(1H-pyrazol-3-yl) pyridine (HL) under hydrothermal conditions, and structurally concluded by single-crystal X-ray diffractions, elemental analyses and IR spectra. The title complex 1 was of triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A novel tetranuclear copper cluster [Cu4(μ-L)6Cl2] was constructed by 2-(1H-pyrazol-3-yl) pyridine (HL) under hydrothermal conditions, and structurally concluded by single-crystal X-ray diffractions, elemental analyses and IR spectra. The title complex 1 was of triclinic system, space group P
2020, 39(5): 955-959
doi: 10.14102/j.cnki.0254-5861.2011-2518
Abstract:
A new complex [Cd(nph)(bix)]n (1, H2nph = 4-nitrophthalic acid, bix = 1, 4-bis(imidazol-1-yl)-benzene) has been successfully synthesized under hydrothermal conditions. Its structure has been characterized by elemental analysis, IR spectrum, TG, single-crystal and powder X-ray diffractions. The Cd2+ ion has a distorted octahedral environment with four O atoms from two nph ligands and two N atoms from two bix ligands. Each bix acts as a cis-conformation bridging ligand to link the neighboring [Cd2(nph)] subunit to form tetranuclear subunits with 42-ring, which are bridged again by bix ligands to yield a two-dimensional network structure. It was stabilized by C–H···O hydrogen bonding and π-π interactions, and extended into a 3D supramolecular architecture. Moreover, the luminescent properties of complex 1 have been investigated in the solid state.
A new complex [Cd(nph)(bix)]n (1, H2nph = 4-nitrophthalic acid, bix = 1, 4-bis(imidazol-1-yl)-benzene) has been successfully synthesized under hydrothermal conditions. Its structure has been characterized by elemental analysis, IR spectrum, TG, single-crystal and powder X-ray diffractions. The Cd2+ ion has a distorted octahedral environment with four O atoms from two nph ligands and two N atoms from two bix ligands. Each bix acts as a cis-conformation bridging ligand to link the neighboring [Cd2(nph)] subunit to form tetranuclear subunits with 42-ring, which are bridged again by bix ligands to yield a two-dimensional network structure. It was stabilized by C–H···O hydrogen bonding and π-π interactions, and extended into a 3D supramolecular architecture. Moreover, the luminescent properties of complex 1 have been investigated in the solid state.
2020, 39(5): 960-966
doi: 10.14102/j.cnki.0254-5861.2011-2537
Abstract:
Two isomorphic 3D lanthanide metal-organic frameworks, {[Tb(L)0.5(OX)0.5(H2O)2DMF].DMF}n (1) and {[Dy(L)0.5(OX)0.5(H2O)2DMF].DMF}n (2), have been prepared under solvothermal conditions based on 1, 4-bis(3, 5-dicarboxylicpyrazol-1-ylmethyl) benzene (H4L), oxalis acid (H2OX) and lanthanide ions. Compound 1 crystallizes in monoclinic system, space group P21/c with a = 9.418(15), b = 15.23(2), c = 14.47(2) Å, β = 100.07(3)°, V = 2044(5) Å3, Z = 4, Mr = 590.3 g/mol, Dc = 1.919 g/cm3, μ = 3.524 mm-1, F(000) = 1168, R = 0.0893 and wR = 0.1902 for 3486 observed reflections (I > 2σ(I)). In compound 1, the central terbium(Ⅲ) ions are coordinated with eight atoms, and two neighboring terbium(Ⅲ) ions are linked together by one bridging oxalic acid group to give rise to a [Tb2(OX)(L)4] unit. Each [Tb2(OX)(L)4] unit connects to the surrounding six identical ones by the oxygen atoms bridging to lead to a 3D framework. Compound 1 exhibits strong luminescent emissions at the solid state owing to the antenna effect of the ligand.
Two isomorphic 3D lanthanide metal-organic frameworks, {[Tb(L)0.5(OX)0.5(H2O)2DMF].DMF}n (1) and {[Dy(L)0.5(OX)0.5(H2O)2DMF].DMF}n (2), have been prepared under solvothermal conditions based on 1, 4-bis(3, 5-dicarboxylicpyrazol-1-ylmethyl) benzene (H4L), oxalis acid (H2OX) and lanthanide ions. Compound 1 crystallizes in monoclinic system, space group P21/c with a = 9.418(15), b = 15.23(2), c = 14.47(2) Å, β = 100.07(3)°, V = 2044(5) Å3, Z = 4, Mr = 590.3 g/mol, Dc = 1.919 g/cm3, μ = 3.524 mm-1, F(000) = 1168, R = 0.0893 and wR = 0.1902 for 3486 observed reflections (I > 2σ(I)). In compound 1, the central terbium(Ⅲ) ions are coordinated with eight atoms, and two neighboring terbium(Ⅲ) ions are linked together by one bridging oxalic acid group to give rise to a [Tb2(OX)(L)4] unit. Each [Tb2(OX)(L)4] unit connects to the surrounding six identical ones by the oxygen atoms bridging to lead to a 3D framework. Compound 1 exhibits strong luminescent emissions at the solid state owing to the antenna effect of the ligand.
2020, 39(5): 967-977
doi: 10.14102/j.cnki.0254-5861.2011-2541
Abstract:
Two 1D and one 3D coordination polymers, namely [Ni2(μ3-deta)(H2biim)3(H2O)2]n (1), {[Zn2(μ4-deta)(phen)2(H2O)]·H2O}n (2) and [Cd2(μ6-deta)(phen)2(H2O)]n (3), have been constructed hydrothermally using H4deta (H4deta = 2, 3, 3΄, 4΄-diphenyl ether tetracarboxylic acid), H2biim (H2biim = 2, 2΄-biimidazole), phen (phen = 1, 10-phenanthroline), and nickel, zinc or cadmium chlorides at 160 ℃. The products were isolated as stable crystalline solids and characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA) and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
Two 1D and one 3D coordination polymers, namely [Ni2(μ3-deta)(H2biim)3(H2O)2]n (1), {[Zn2(μ4-deta)(phen)2(H2O)]·H2O}n (2) and [Cd2(μ6-deta)(phen)2(H2O)]n (3), have been constructed hydrothermally using H4deta (H4deta = 2, 3, 3΄, 4΄-diphenyl ether tetracarboxylic acid), H2biim (H2biim = 2, 2΄-biimidazole), phen (phen = 1, 10-phenanthroline), and nickel, zinc or cadmium chlorides at 160 ℃. The products were isolated as stable crystalline solids and characterized by IR spectra, elemental analyses, thermogravimetric analyses (TGA) and single-crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system, space group P
2020, 39(5): 978-982
doi: 10.14102/j.cnki.0254-5861.2011-2579
Abstract:
A novel dinuclear copper(Ⅱ) coordination compound, [CuⅡ(Hpdc)(phen)Cl][CuⅡ(pdc)(phen)]·4H2O (1, H2pdc = pyridine-2, 6-dicarboxylic acid, phen = 1, 10-phenanthroline), has been obtained by an ionothermal method using the ionic liquid 3-butyl-1-methylimidazolium bromide ([Bmim]Br) as solvent, and fully characterized by elemental analyses, energy-dispersive X-ray spectroscopy (EDX), IR and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A novel dinuclear copper(Ⅱ) coordination compound, [CuⅡ(Hpdc)(phen)Cl][CuⅡ(pdc)(phen)]·4H2O (1, H2pdc = pyridine-2, 6-dicarboxylic acid, phen = 1, 10-phenanthroline), has been obtained by an ionothermal method using the ionic liquid 3-butyl-1-methylimidazolium bromide ([Bmim]Br) as solvent, and fully characterized by elemental analyses, energy-dispersive X-ray spectroscopy (EDX), IR and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group P
