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2020 Volume 39 Issue 11
2020, 39(11): 1925-1932
doi: 10.14102/j.cnki.0254–5861.2011–2833
Abstract:
Hexachlorocyclopentadiene (HCCP) is one of the chlorinated and highly reactive pollutants, which can be released into the atmosphere and undergo chemical transformations. In this paper, the initiated reaction mechanisms of HCCP with typical atmospheric oxidants (•NO3, •HO2, •OH, and O3) were theoretically investigated. The results mean that all initiated reactions are exothermic, and the energy barriers do not exceed 16 kcal⋅mol-1. The rate constants of HCCP reaction triggered by •NO3, •HO2, •OH, and O3 are 2.49 × 10-12, 2.44 × 10-22, 2.46 × 10-13 and 1.33 × 10-20 cm3⋅molecule-1⋅s-1 at 298 K, respectively. It can be concluded that the reaction of •NO3 and •OH with HCCP more likely occurs according to the rate constants. Then the subsequent reactions of the •NO3/•OH-initiated intermediates with O2 and NO were calculated, resulting in that the cyclopentadiene is ruptured completely. And the results show that the Criegee intermediates created in the ozonization reactions of HCCP can react with O2, NO2 and SO2. This study gives more insight into the chemical transformation mechanisms of HCCP in the atmosphere.
Hexachlorocyclopentadiene (HCCP) is one of the chlorinated and highly reactive pollutants, which can be released into the atmosphere and undergo chemical transformations. In this paper, the initiated reaction mechanisms of HCCP with typical atmospheric oxidants (•NO3, •HO2, •OH, and O3) were theoretically investigated. The results mean that all initiated reactions are exothermic, and the energy barriers do not exceed 16 kcal⋅mol-1. The rate constants of HCCP reaction triggered by •NO3, •HO2, •OH, and O3 are 2.49 × 10-12, 2.44 × 10-22, 2.46 × 10-13 and 1.33 × 10-20 cm3⋅molecule-1⋅s-1 at 298 K, respectively. It can be concluded that the reaction of •NO3 and •OH with HCCP more likely occurs according to the rate constants. Then the subsequent reactions of the •NO3/•OH-initiated intermediates with O2 and NO were calculated, resulting in that the cyclopentadiene is ruptured completely. And the results show that the Criegee intermediates created in the ozonization reactions of HCCP can react with O2, NO2 and SO2. This study gives more insight into the chemical transformation mechanisms of HCCP in the atmosphere.
2020, 39(11): 1933-1940
doi: 10.14102/j.cnki.0254–5861.2011–2840
Abstract:
The excited-state intramolecular proton transfer (ESIPT) mechanisms of 2-(2-hydroxyphenyl)-4-phenylthiazole (HPT) and 2-(5-bromo-2-hydroxyphenyl)-4-phenylthiazole (BrHPT) have been systematically investigated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, approaching along with the polarizable continuum model (PCM). The calculated primary bond lengths and bond angles demonstrate that HPT and BrHPT can form intramolecular hydrogen bonds in the ground state (S0), which can be significantly strengthened in the first excited state (S1). Our calculated results well reproduce the experimental absorption and emission spectra. Upon addition of F-, the proton can move close to F- and the hydroxy moieties are deprotonated, which cause a red-shift in absorption and a new emission peak in fluorescence emission with the disappearance of the dual fluorescence emission. The calculated Mulliken's charge distribution and frontier molecular orbitals further demonstrate that the ESIPT processes are more likely to occur in the S1 state. The constructed potential energy curves of the S0 and S1 states confirm that the proton transfer processes are hard to occur in the S0 state due to the high energy barriers. Moreover, much lower energy barriers are found in the S1 state, which proves that the ESIPT processes are more likely to take place in the S1 state. In addition, compound with electron withdrawing (–Br) group might result in much stronger intramolecular hydrogen bond and owns lower energy barrier, which can facilitate the ESIPT processes.
The excited-state intramolecular proton transfer (ESIPT) mechanisms of 2-(2-hydroxyphenyl)-4-phenylthiazole (HPT) and 2-(5-bromo-2-hydroxyphenyl)-4-phenylthiazole (BrHPT) have been systematically investigated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, approaching along with the polarizable continuum model (PCM). The calculated primary bond lengths and bond angles demonstrate that HPT and BrHPT can form intramolecular hydrogen bonds in the ground state (S0), which can be significantly strengthened in the first excited state (S1). Our calculated results well reproduce the experimental absorption and emission spectra. Upon addition of F-, the proton can move close to F- and the hydroxy moieties are deprotonated, which cause a red-shift in absorption and a new emission peak in fluorescence emission with the disappearance of the dual fluorescence emission. The calculated Mulliken's charge distribution and frontier molecular orbitals further demonstrate that the ESIPT processes are more likely to occur in the S1 state. The constructed potential energy curves of the S0 and S1 states confirm that the proton transfer processes are hard to occur in the S0 state due to the high energy barriers. Moreover, much lower energy barriers are found in the S1 state, which proves that the ESIPT processes are more likely to take place in the S1 state. In addition, compound with electron withdrawing (–Br) group might result in much stronger intramolecular hydrogen bond and owns lower energy barrier, which can facilitate the ESIPT processes.
2020, 39(11): 1941-1948
doi: 10.14102/j.cnki.0254–5861.2011–2738
Abstract:
Solid polymer electrolytes (SPEs) have been considered as the spotlight in recent years due to their high safety, non-flammability and good flexibility. Nonetheless, high crystallinity of polymer matrix leads to low ionic conductivity at ambient conditions and retards the practical applications of SPEs. Herein, we report hybrid solid electrolytes (HSE) containing bulky LATP in poly(ethylene oxide) (PEO) matrix, which significantly enhances the electrochemical properties. LATP has been easily obtained by an accessible solid-state method. The solid electrolyte based on 20 wt% LATP in PEO polymer matrix (abbreviated as PEO-20) exhibits an ionic conductivity of 2.1 ×10–5 S·cm–1 at 30 ℃, an order of magnitude higher than 2.9 × 10–6 S·cm–1 of the pristine PEO solid electrolyte (abbreviated as PEO–0), mainly resulting from the decline of crystallinity in polymer matrix. The electrochemical window of PEO-20 can reach 4.84 V at room temperature, compared with 4.40 V for PEO-0, which could be compatible with high-voltage cathode materials.
Solid polymer electrolytes (SPEs) have been considered as the spotlight in recent years due to their high safety, non-flammability and good flexibility. Nonetheless, high crystallinity of polymer matrix leads to low ionic conductivity at ambient conditions and retards the practical applications of SPEs. Herein, we report hybrid solid electrolytes (HSE) containing bulky LATP in poly(ethylene oxide) (PEO) matrix, which significantly enhances the electrochemical properties. LATP has been easily obtained by an accessible solid-state method. The solid electrolyte based on 20 wt% LATP in PEO polymer matrix (abbreviated as PEO-20) exhibits an ionic conductivity of 2.1 ×10–5 S·cm–1 at 30 ℃, an order of magnitude higher than 2.9 × 10–6 S·cm–1 of the pristine PEO solid electrolyte (abbreviated as PEO–0), mainly resulting from the decline of crystallinity in polymer matrix. The electrochemical window of PEO-20 can reach 4.84 V at room temperature, compared with 4.40 V for PEO-0, which could be compatible with high-voltage cathode materials.
2020, 39(11): 1949-1957
doi: 10.14102/j.cnki.0254–5861.2011–2740
Abstract:
Humidity sensors have been widely applied to detect environment humidity in various fields. However, most of humidity sensors cannot provide performance needed for high sensitivity and fast response. We report one type of capacitive-type humidity sensors composed of laser-scribed graphene (LSG) as sensing electrodes and graphene oxide/tin dioxide (GO/SnO2) as a sensing layer. The LSG is reduced graphene oxide (rGO) electrodes resulted from selective reducing of GO within a GO/SnO2 composite layer by laser scribing method, and the sensing layer is the un-scribed GO/SnO2 composite. The sensor fabrication is a one-step process which is facile and cost-efficient. When a mass ratio of GO: SnO2 in the composite reaches 1:1, the humidity sensor (named as LSG-GS1) has the best properties than other ratios, which exhibits high sensitivity in the range of 11%~97% relative humidity (RH). In addition, the LSG-GS1 also has very quick response/recovery time (20 s for adsorption and 18 s for desorption) when RH changes from 23% to 84%, and very good stability after monitoring for 41 days. Such excellent performances of the humidity sensor can be attributed to synergistic effect of SnO2 and GO within the composite layer.
Humidity sensors have been widely applied to detect environment humidity in various fields. However, most of humidity sensors cannot provide performance needed for high sensitivity and fast response. We report one type of capacitive-type humidity sensors composed of laser-scribed graphene (LSG) as sensing electrodes and graphene oxide/tin dioxide (GO/SnO2) as a sensing layer. The LSG is reduced graphene oxide (rGO) electrodes resulted from selective reducing of GO within a GO/SnO2 composite layer by laser scribing method, and the sensing layer is the un-scribed GO/SnO2 composite. The sensor fabrication is a one-step process which is facile and cost-efficient. When a mass ratio of GO: SnO2 in the composite reaches 1:1, the humidity sensor (named as LSG-GS1) has the best properties than other ratios, which exhibits high sensitivity in the range of 11%~97% relative humidity (RH). In addition, the LSG-GS1 also has very quick response/recovery time (20 s for adsorption and 18 s for desorption) when RH changes from 23% to 84%, and very good stability after monitoring for 41 days. Such excellent performances of the humidity sensor can be attributed to synergistic effect of SnO2 and GO within the composite layer.
2020, 39(11): 1958-1964
doi: 10.14102/j.cnki.0254–5861.2011–2742
Abstract:
The aluminum based MOFs compound, MIL-96(Al), has been studied as a luminescence sensor by incorporating of Eu3+ ions, which renders the compound strong red-light emission. The as-synthesized MIL-96(Al): Eu3+ nanocrystals exhibit water dispersibility and environmental stability, which are general requirement for an ideal sensing material. The MIL-96(Al): Eu3+ nanocrystals show excellent selective detection ability on Fe3+ ions in aqueous solution with value of low detection limit 20 μM. Meanwhile, it also exhibits excellent selective detection ability on CrO42- and Cr2O72- in aqueous solution with value of low detection limit 10 and 22 μM, respectively. The results of this study show that MIL-96(Al): Eu3+ nanocrystals could be used as a multi-responsive luminescent senor for Fe3+ and Cr(VI) species in aqueous solution. The possible luminescence quenching mechanism has also been discussed.
The aluminum based MOFs compound, MIL-96(Al), has been studied as a luminescence sensor by incorporating of Eu3+ ions, which renders the compound strong red-light emission. The as-synthesized MIL-96(Al): Eu3+ nanocrystals exhibit water dispersibility and environmental stability, which are general requirement for an ideal sensing material. The MIL-96(Al): Eu3+ nanocrystals show excellent selective detection ability on Fe3+ ions in aqueous solution with value of low detection limit 20 μM. Meanwhile, it also exhibits excellent selective detection ability on CrO42- and Cr2O72- in aqueous solution with value of low detection limit 10 and 22 μM, respectively. The results of this study show that MIL-96(Al): Eu3+ nanocrystals could be used as a multi-responsive luminescent senor for Fe3+ and Cr(VI) species in aqueous solution. The possible luminescence quenching mechanism has also been discussed.
2020, 39(11): 1965-1972
doi: 10.14102/j.cnki.0254–5861.2011–2747
Abstract:
Diorganotin 2-(2-(4-methoxybenzoyl)hydrazono)-3-phenylpropanoic carboxylate complexes I {[p-CH3O-C6H4O(O)C=N-N=C(PhCH2)COO](n-Bu)2Sn(CH3OH)}2 and II {[p-CH3O-C6H4O(O)C=N-N=C(PhCH2)COO](PhCH2)2Sn(CH3OH)}2 have been synthesized. The complexes have been characterized by IR, 1H, 13C and 119Sn NMR spectra, HRMS, elemental analysis, thermal stability analysis and the crystal structures have been determined by X-ray diffraction. The crystal of complex I belongs to triclinic system, space group P\begin{document}$ \overline 1 $\end{document} \begin{document}$ \overline 1 $\end{document}
Diorganotin 2-(2-(4-methoxybenzoyl)hydrazono)-3-phenylpropanoic carboxylate complexes I {[p-CH3O-C6H4O(O)C=N-N=C(PhCH2)COO](n-Bu)2Sn(CH3OH)}2 and II {[p-CH3O-C6H4O(O)C=N-N=C(PhCH2)COO](PhCH2)2Sn(CH3OH)}2 have been synthesized. The complexes have been characterized by IR, 1H, 13C and 119Sn NMR spectra, HRMS, elemental analysis, thermal stability analysis and the crystal structures have been determined by X-ray diffraction. The crystal of complex I belongs to triclinic system, space group P
2020, 39(11): 1973-1977
doi: 10.14102/j.cnki.0254–5861.2011–2720
Abstract:
The title compound, C16H11F4N3O2, was synthesized and structurally characterized by elemental analysis, IR, MS, 1H-NMR and single-crystal X-ray diffraction. This compound has a pyrazolo[1, 5-a]pyrimidine skeleton, and it crystallizes in monoclinic system, space group P21/c with a = 20.8547(12), b = 20.5558(10), c = 7.1575(4) Å, β = 96.610(5)°, V = 3047.9(3) Å3, Z = 4, Dc = 1.540 g·cm–3, F(000) = 1440, μ(MoKα) = 0.14 mm–1, R = 0.0546 and wR = 0.1276 for 5370 reflections with I > 2σ(I). In addition, biological activity determination results indicated that the title compound exhibited poor inhibitory activity on MKN45 and H460 cancer cell lines.
The title compound, C16H11F4N3O2, was synthesized and structurally characterized by elemental analysis, IR, MS, 1H-NMR and single-crystal X-ray diffraction. This compound has a pyrazolo[1, 5-a]pyrimidine skeleton, and it crystallizes in monoclinic system, space group P21/c with a = 20.8547(12), b = 20.5558(10), c = 7.1575(4) Å, β = 96.610(5)°, V = 3047.9(3) Å3, Z = 4, Dc = 1.540 g·cm–3, F(000) = 1440, μ(MoKα) = 0.14 mm–1, R = 0.0546 and wR = 0.1276 for 5370 reflections with I > 2σ(I). In addition, biological activity determination results indicated that the title compound exhibited poor inhibitory activity on MKN45 and H460 cancer cell lines.
2020, 39(11): 1978-1984
doi: 10.14102/j.cnki.0254–5861.2011–2703
Abstract:
A three-dimensional quantitative structure-activity relationship (3D-QSAR) study was conducted to analyze the A1AR density (Bmax) of 56 3-aroyl-5-substituted thiophene derivatives (ASTDs) in human A1 Chinese hamster ovary (hA1CHO) membranes by the comparative molecular field analysis (CoMFA) method. A training set of 45 compounds was used to establish the predictive model, which was verified by the test set of 17 compounds containing template molecule and 5 newly designed molecules. The cross-validation (Rcv2) and non-cross-validation (R2) coefficients of the training set were 0.655 and 0.959, respectively. The model was used to predict the activities of the compounds of the training and test sets, and the results indicated that the models had strong stability and good prediction ability. According to model analysis, the contribution of steric and electrostatic fields was 51.4% and 48.6%, respectively. Based on the 3D contour maps, five excellent ASTDs agonists were designed, which need to be further verified by biomedical experiments.
A three-dimensional quantitative structure-activity relationship (3D-QSAR) study was conducted to analyze the A1AR density (Bmax) of 56 3-aroyl-5-substituted thiophene derivatives (ASTDs) in human A1 Chinese hamster ovary (hA1CHO) membranes by the comparative molecular field analysis (CoMFA) method. A training set of 45 compounds was used to establish the predictive model, which was verified by the test set of 17 compounds containing template molecule and 5 newly designed molecules. The cross-validation (Rcv2) and non-cross-validation (R2) coefficients of the training set were 0.655 and 0.959, respectively. The model was used to predict the activities of the compounds of the training and test sets, and the results indicated that the models had strong stability and good prediction ability. According to model analysis, the contribution of steric and electrostatic fields was 51.4% and 48.6%, respectively. Based on the 3D contour maps, five excellent ASTDs agonists were designed, which need to be further verified by biomedical experiments.
2020, 39(11): 1985-1989
doi: 10.14102/j.cnki.0254–5861.2011–2696
Abstract:
Comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) for imidazopyrimidine derivatives were performed to get the molecular active conformation selection, molecular alignment, as well as the establishment of corresponding 3D-QSAR model. The model established by this method has good ability to predict such compounds. For CoMFA model, the cross-validated q2 and non-cross-validated r2 values are 0.665 and 0.872, respectively. The best q2 value for CoMSIA model is 0.632 and r2 value is 0.923. Using this information and the three-dimensional equipotential map for molecular design can theoretically obtain some new antibacterial drugs with higher activity. There are two newly designed molecules with activity values of 7.921 and 7.872, which are higher than that of the template molecule No. 12 with an activity value of 7.850, and the QSAR research results can provide a theoretical reference for the synthesis of new drugs.
Comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) for imidazopyrimidine derivatives were performed to get the molecular active conformation selection, molecular alignment, as well as the establishment of corresponding 3D-QSAR model. The model established by this method has good ability to predict such compounds. For CoMFA model, the cross-validated q2 and non-cross-validated r2 values are 0.665 and 0.872, respectively. The best q2 value for CoMSIA model is 0.632 and r2 value is 0.923. Using this information and the three-dimensional equipotential map for molecular design can theoretically obtain some new antibacterial drugs with higher activity. There are two newly designed molecules with activity values of 7.921 and 7.872, which are higher than that of the template molecule No. 12 with an activity value of 7.850, and the QSAR research results can provide a theoretical reference for the synthesis of new drugs.
Structure-based Screening for the Non-zinc-chelating Selective MMP-13 Inhibitors of Natural Products
2020, 39(11): 1990-2000
doi: 10.14102/j.cnki.0254–5861.2011–2831
Abstract:
Matrix metalloproteinase-13 (MMP-13) has been considered as a promising therapeutic target for osteoarthritis. In this work, the experimental crystal structures of five MMP-13-ligand complexes are used to build the multiple structure-based pharmacophore model of MMP-13 inhibitors. The reliability of pharmacophore model is validated using a decoy set. The pharmacophore model contains four chemical features: two hydrogen bond acceptor (HBA), one hydrophobic (HY) feature, and one ring aromatic (RA) feature. Particularly, the HY feature is found to orient the MMP-13 inhibitors deep into the S1' pocket of MMP-13 to produce selective inhibition. By carrying out the screening of pharmacophore model and subsequent molecular docking, the four non-zinc-chelating selective MMP-13 inhibitors of natural products (NP-015973, NP-000814, STOCK1N-24933, and STOCK1N-69443) are identified. It is found that the binding modes of MMP-13 with our screened four natural products are very similar to the reported experimental binding mode of MMP-13 with the most active inhibitor (GG12003, IC50: 0.67 nM), and each of them involves the interactions of a ligand with the three amino acid residues Thr226, Lys119, and His201 of MMP-13 receptor. This shows that our modeling results are in good agreement with the relevant experimental results, which strongly supports our screened MMP-13 inhibitors of natural products. These screened natural products may be used as the lead compounds of MMP-13 inhibitors in the future studies of structural modifications.
Matrix metalloproteinase-13 (MMP-13) has been considered as a promising therapeutic target for osteoarthritis. In this work, the experimental crystal structures of five MMP-13-ligand complexes are used to build the multiple structure-based pharmacophore model of MMP-13 inhibitors. The reliability of pharmacophore model is validated using a decoy set. The pharmacophore model contains four chemical features: two hydrogen bond acceptor (HBA), one hydrophobic (HY) feature, and one ring aromatic (RA) feature. Particularly, the HY feature is found to orient the MMP-13 inhibitors deep into the S1' pocket of MMP-13 to produce selective inhibition. By carrying out the screening of pharmacophore model and subsequent molecular docking, the four non-zinc-chelating selective MMP-13 inhibitors of natural products (NP-015973, NP-000814, STOCK1N-24933, and STOCK1N-69443) are identified. It is found that the binding modes of MMP-13 with our screened four natural products are very similar to the reported experimental binding mode of MMP-13 with the most active inhibitor (GG12003, IC50: 0.67 nM), and each of them involves the interactions of a ligand with the three amino acid residues Thr226, Lys119, and His201 of MMP-13 receptor. This shows that our modeling results are in good agreement with the relevant experimental results, which strongly supports our screened MMP-13 inhibitors of natural products. These screened natural products may be used as the lead compounds of MMP-13 inhibitors in the future studies of structural modifications.
2020, 39(11): 2001-2008
doi: 10.14102/j.cnki.0254–5861.2011–2734
Abstract:
Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide (Ln3+)-doped luminescent nanocrystals (NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall (< 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ~10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation (e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence (UCL) ranging from ultraviolet (UV) to visible and to near-infrared (NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.
Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide (Ln3+)-doped luminescent nanocrystals (NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall (< 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ~10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation (e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence (UCL) ranging from ultraviolet (UV) to visible and to near-infrared (NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.
2020, 39(11): 2009-2015
doi: 10.14102/j.cnki.0254–5861.2011–2750
Abstract:
An unprecedented one-dimensional coordination polymer [Ag2(PhPO3H)2(DPPP)]n (1) based on phenylphosphonic acid (PhPO3H2) and 1, 3-bis(diphenyphosphino)propane (DPPP) has been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the complex crystallizes in triclinic system, space group P1. The coordination geometry of each Ag(I) ion is planar trigonal. Two kinds of rings were found in 1, such as the four-membered ring with Ag2O2 and the eight-membered ring with Ag2O4P2 constructed by PhPO3H– ligands, which were then connected by DPPP ligands forming a zigzag type chain. Moreover, the light absorption and luminescent property of 1 were also investigated.
An unprecedented one-dimensional coordination polymer [Ag2(PhPO3H)2(DPPP)]n (1) based on phenylphosphonic acid (PhPO3H2) and 1, 3-bis(diphenyphosphino)propane (DPPP) has been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the complex crystallizes in triclinic system, space group P1. The coordination geometry of each Ag(I) ion is planar trigonal. Two kinds of rings were found in 1, such as the four-membered ring with Ag2O2 and the eight-membered ring with Ag2O4P2 constructed by PhPO3H– ligands, which were then connected by DPPP ligands forming a zigzag type chain. Moreover, the light absorption and luminescent property of 1 were also investigated.
2020, 39(11): 2016-2020
doi: 10.14102/j.cnki.0254–5861.2011–2827
Abstract:
A new binuclear cage-like yttrium(III) complex Y2(TMBA)6(phen)2 (1) with yttrium nitrate, 2, 4, 6-trimethylbenzoic acid (TMBA) and 1, 10-phenanthroline (phen) was synthesized. It crystallizes in the triclinic space group P\begin{document}$ \overline 1 $\end{document}
A new binuclear cage-like yttrium(III) complex Y2(TMBA)6(phen)2 (1) with yttrium nitrate, 2, 4, 6-trimethylbenzoic acid (TMBA) and 1, 10-phenanthroline (phen) was synthesized. It crystallizes in the triclinic space group P
2020, 39(11): 2021-2026
doi: 10.14102/j.cnki.0254–5861.2011–2739
Abstract:
A novel copper(I) coordination polymer [C30H18Cu3Cl3N4]n was solvethermally synthesized with 1-(prop-2-en-1-yl)-2-{4-[1-(prop-2-en-1-yl)-1H-1, 3-benzodiazol-2-yl]phenyl}-1H-1, 3-benzodiazole as the flexible ligand. It crystalizes in orthorhombic system, space group Pbcn with a = 22.0890(7), b = 6.3626(2), c = 18.2480(6) Å, V = 2564.64(14) Å3 and Mr = 365.73. The compound characterized by elemental analysis, infrared spectroscopy and powder X-ray diffraction analysis displays a 2D structure. The complex shows strong green luminescence at 506 nm and better property of electrochemical oxygen evolution.
A novel copper(I) coordination polymer [C30H18Cu3Cl3N4]n was solvethermally synthesized with 1-(prop-2-en-1-yl)-2-{4-[1-(prop-2-en-1-yl)-1H-1, 3-benzodiazol-2-yl]phenyl}-1H-1, 3-benzodiazole as the flexible ligand. It crystalizes in orthorhombic system, space group Pbcn with a = 22.0890(7), b = 6.3626(2), c = 18.2480(6) Å, V = 2564.64(14) Å3 and Mr = 365.73. The compound characterized by elemental analysis, infrared spectroscopy and powder X-ray diffraction analysis displays a 2D structure. The complex shows strong green luminescence at 506 nm and better property of electrochemical oxygen evolution.
2020, 39(11): 2027-2032
doi: 10.14102/j.cnki.0254–5861.2011–2741
Abstract:
An interesting metal-organic framework (MOF) PFC-31 was synthesized by a simple solvothermal reaction. X-ray crystallography reveals that PFC-31 crystallizes in monoclinic system, space group P21/c with a = 6.8410(17), b = 20.123(5), c = 7.689(2) Å, β = 104.239(7)°, V = 1026.0(5) Å3, Z = 2, C16H22CuN4O8S2, Mr = 526.03, μ = 1.322 mm–1, Dc = 1.703 g/cm3, F(000) = 542, GOOF = 1.214, R = 0.0975 and wR = 0.2324. According to X-ray analysis, PFC-31 shows one-dimensional chain constructed by Cu(II) centers coordinating with two pyridine groups, two sulfonate groups and two DMF molecules. Owing to the orderly functionalized sulfonate group and Lewis metal sites, PFC-31 exhibits good catalytic capability for CO2 cycloaddition of epoxide under normal pressure and temperature.
An interesting metal-organic framework (MOF) PFC-31 was synthesized by a simple solvothermal reaction. X-ray crystallography reveals that PFC-31 crystallizes in monoclinic system, space group P21/c with a = 6.8410(17), b = 20.123(5), c = 7.689(2) Å, β = 104.239(7)°, V = 1026.0(5) Å3, Z = 2, C16H22CuN4O8S2, Mr = 526.03, μ = 1.322 mm–1, Dc = 1.703 g/cm3, F(000) = 542, GOOF = 1.214, R = 0.0975 and wR = 0.2324. According to X-ray analysis, PFC-31 shows one-dimensional chain constructed by Cu(II) centers coordinating with two pyridine groups, two sulfonate groups and two DMF molecules. Owing to the orderly functionalized sulfonate group and Lewis metal sites, PFC-31 exhibits good catalytic capability for CO2 cycloaddition of epoxide under normal pressure and temperature.
2020, 39(11): 2033-2040
doi: 10.14102/j.cnki.0254–5861.2011–2743
Abstract:
Porous single crystals would significantly enhance their catalysis functionalities owing to the combination of structural coherence and porous microstructures. Porous single crystals have wormhole microstructures and then we define them as wormcrystals. The twisted surfaces in porous microstructures would produce surface lattice distortions that give rise to high-energy active surfaces. Here we grow porous iron single crystals at an unprecedented 2 cm scale with a lattice reconstruction strategy and create high-energy surfaces through the control of lattice distortions within a thickness region of 1~2 nm. The porous iron crystal therefore boosts electrochemical reduction of nitrobenzene to aminobenzene with ~100% conversion and > 95% selectivity. The exceptionally high current densities with porous iron crystals represent the first level electrocatalysis performance. The current work would open a new pathway not only to the creation of high energy surfaces but also to the growth of porous single crystals at large scales in wealth of other materials.
Porous single crystals would significantly enhance their catalysis functionalities owing to the combination of structural coherence and porous microstructures. Porous single crystals have wormhole microstructures and then we define them as wormcrystals. The twisted surfaces in porous microstructures would produce surface lattice distortions that give rise to high-energy active surfaces. Here we grow porous iron single crystals at an unprecedented 2 cm scale with a lattice reconstruction strategy and create high-energy surfaces through the control of lattice distortions within a thickness region of 1~2 nm. The porous iron crystal therefore boosts electrochemical reduction of nitrobenzene to aminobenzene with ~100% conversion and > 95% selectivity. The exceptionally high current densities with porous iron crystals represent the first level electrocatalysis performance. The current work would open a new pathway not only to the creation of high energy surfaces but also to the growth of porous single crystals at large scales in wealth of other materials.
2020, 39(11): 2041-2045
doi: 10.14102/j.cnki.0254–5861.2011–2736
Abstract:
A one-dimensional (1D) coordination polymer, [Cd2(TFBPDC)2(ad)2(CH3OH)2]n (1), based on the 3, 3΄, 5, 5΄-tetrafluorobiphenyl-4, 4΄-dicarboxylate (TFBPDC2–) and adenine (ad) ligands, was synthesized. Compound 1 crystallizes in the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A one-dimensional (1D) coordination polymer, [Cd2(TFBPDC)2(ad)2(CH3OH)2]n (1), based on the 3, 3΄, 5, 5΄-tetrafluorobiphenyl-4, 4΄-dicarboxylate (TFBPDC2–) and adenine (ad) ligands, was synthesized. Compound 1 crystallizes in the triclinic system, space group P
2020, 39(11): 2046-2052
doi: 10.14102/j.cnki.0254–5861.2011–2847
Abstract:
A novel tetra-nuclear Nd(III) coordination polymer, Nd4(µ3-OH)4(µ2-H2O)2(C6H4NO2)6(N3)2(H2O)2 (1, C6H4N zide anion), was successfully prepared under hydrothermal conditions and fully characterized by C, H and N elemental analysis, IR spectrum, thermal stability and single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A novel tetra-nuclear Nd(III) coordination polymer, Nd4(µ3-OH)4(µ2-H2O)2(C6H4NO2)6(N3)2(H2O)2 (1, C6H4N zide anion), was successfully prepared under hydrothermal conditions and fully characterized by C, H and N elemental analysis, IR spectrum, thermal stability and single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P
