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2015 Volume 31 Issue 7
2015, 31(7): 1269-1277
doi: 10.11862/CJIC.2015.180
Abstract:
The self-inclusion of maleonitriledithiolate-modified β-Cyclodextrin (mono[6-deoxy-6-(2-butene-dinitrile-2,3-dimercapto)]-β-Cyclodextrin, 6-mnt-β-Cyclodextrin) was studied by circular dichroism (CD) spectroscopy, 1H NMR spectroscopy, isothermal titration calorimetry (ITC), and chemical titration methods. Chemical titration results indicate that sodium dodecyl sulfate (SDS) is able to effectively dissociate the configuration of 6-mnt-β-Cyclodextrin, as well as Cu2+ and Co2+ do in solution. The experimental data suggest that 6-mnt-β-Cyclodextrin prefers self-inclusion in aqueous solution, which could be reversibly unlocked by metal ions. In its unlocked conformation, 6-mnt-β-Cyclodextrin is able to include Neutral Red (NR) and exhibits host-guest interactions. Upon removal of the "key" metal ion, 6-mnt-β-Cyclodextrin liberates the guest molecule and restores its self-inclusion. Therefore, the maleonitriledithiolate-modified cyclodextrin host exhibits potential to controllably uptake and release its guest by selected metal ion coordination.
The self-inclusion of maleonitriledithiolate-modified β-Cyclodextrin (mono[6-deoxy-6-(2-butene-dinitrile-2,3-dimercapto)]-β-Cyclodextrin, 6-mnt-β-Cyclodextrin) was studied by circular dichroism (CD) spectroscopy, 1H NMR spectroscopy, isothermal titration calorimetry (ITC), and chemical titration methods. Chemical titration results indicate that sodium dodecyl sulfate (SDS) is able to effectively dissociate the configuration of 6-mnt-β-Cyclodextrin, as well as Cu2+ and Co2+ do in solution. The experimental data suggest that 6-mnt-β-Cyclodextrin prefers self-inclusion in aqueous solution, which could be reversibly unlocked by metal ions. In its unlocked conformation, 6-mnt-β-Cyclodextrin is able to include Neutral Red (NR) and exhibits host-guest interactions. Upon removal of the "key" metal ion, 6-mnt-β-Cyclodextrin liberates the guest molecule and restores its self-inclusion. Therefore, the maleonitriledithiolate-modified cyclodextrin host exhibits potential to controllably uptake and release its guest by selected metal ion coordination.
2015, 31(7): 1278-1286
doi: 10.11862/CJIC.2015.185
Abstract:
A novel kind of coordination molecular corners [M2L2] ([1=(bpy)Pd]2L2, 2=[(dmbpy)Pd]2L2, 3=[(phen)Pd]2L2, 4=[(ppy)Pt]2L2, where bpy=2,2'-bipyridine, dmbpy=4,4'-dimethyl-2,2'-bipyridine, phen=1,10-phenanthroline, ppy=2-phenylpyridine) was synthesized through synergistic metal-metal bonding interaction and spontaneous deprotonation from the pyrazole linkers 4-(4-(anthracen-9-yl)phenyl)-3,5-dimethyl-1H-pyrazole (L). Three complexes 1~3 were characterized by single crystal X-ray diffraction, 1H and 13C NMR, ESI-MS and fluorescence spectroscopy. The neutral organometallic corner [(ppy)Pt]2L2 4 was also determined by 1H and 13C NMR, MALDI-TOF-MS and fluorescence spectroscopy. These achiral molecular corners assemble from different achiral dimetallic centers with the achiral ligand HL in quite different crystal structures, in particular, 3 with a [(phen)Pd]2 assembling center crystallizes into a supramolecular chiral architecture.
A novel kind of coordination molecular corners [M2L2] ([1=(bpy)Pd]2L2, 2=[(dmbpy)Pd]2L2, 3=[(phen)Pd]2L2, 4=[(ppy)Pt]2L2, where bpy=2,2'-bipyridine, dmbpy=4,4'-dimethyl-2,2'-bipyridine, phen=1,10-phenanthroline, ppy=2-phenylpyridine) was synthesized through synergistic metal-metal bonding interaction and spontaneous deprotonation from the pyrazole linkers 4-(4-(anthracen-9-yl)phenyl)-3,5-dimethyl-1H-pyrazole (L). Three complexes 1~3 were characterized by single crystal X-ray diffraction, 1H and 13C NMR, ESI-MS and fluorescence spectroscopy. The neutral organometallic corner [(ppy)Pt]2L2 4 was also determined by 1H and 13C NMR, MALDI-TOF-MS and fluorescence spectroscopy. These achiral molecular corners assemble from different achiral dimetallic centers with the achiral ligand HL in quite different crystal structures, in particular, 3 with a [(phen)Pd]2 assembling center crystallizes into a supramolecular chiral architecture.
2015, 31(7): 1287-1295
doi: 10.11862/CJIC.2015.162
Abstract:
A nano-sized Ru catalyst was prepared using the precipitation method. The performance of the catalyst for selective hydrogenation of benzene to cyclohexene with Na2SiO3·9H2O and diethanolamine as modifiers was investigated in the presence of ZnSO4. The catalyst after and before hydrogenation was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS). The results show that Na2SiO3 in the solution could react with ZnSO4 to form a Zn4Si2O7(OH)2H2O salt, H2SO4 and Na2SO4, and the Zn4Si2O7(OH)2H2O salt chemisorbed on the surface of the Ru catalyst plays a key role in improving the selectivity to cyclohexene of the Ru catalyst. The increased dosage of Na2SiO3·9H2O will result in the increased amount of the formed Zn4Si2O7(OH)2H2O salt, the decreased activity of the Ru catalyst and the increased selectivity to cyclohexene. The diethanolamine added into the slurry could neutralize the H2SO4 formed by reacting Na2SiO3 with ZnSO4. This could shift the chemical equilibrium to the direction of the formation of the Zn4Si2O7(OH)2H2O salt, resulting in the increase of the selectivity to cyclohexene of the Ru catalyst. When the mass ratio of the Ru catalyst, ZnSO4·7H2O, Na2SiO3·9H2O, diethanolamine and the dispersant ZrO2 was at 1.0:24.6:0.4:0.2:5.0, 2 g of the Ru catalyst will give a selectivity to cyclohexene of 75% and a cyclohexene yield of 55% at a benzene conversion of 73%. Moreover, this catalytic system shows a good reusability and an excellent stability.
A nano-sized Ru catalyst was prepared using the precipitation method. The performance of the catalyst for selective hydrogenation of benzene to cyclohexene with Na2SiO3·9H2O and diethanolamine as modifiers was investigated in the presence of ZnSO4. The catalyst after and before hydrogenation was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS). The results show that Na2SiO3 in the solution could react with ZnSO4 to form a Zn4Si2O7(OH)2H2O salt, H2SO4 and Na2SO4, and the Zn4Si2O7(OH)2H2O salt chemisorbed on the surface of the Ru catalyst plays a key role in improving the selectivity to cyclohexene of the Ru catalyst. The increased dosage of Na2SiO3·9H2O will result in the increased amount of the formed Zn4Si2O7(OH)2H2O salt, the decreased activity of the Ru catalyst and the increased selectivity to cyclohexene. The diethanolamine added into the slurry could neutralize the H2SO4 formed by reacting Na2SiO3 with ZnSO4. This could shift the chemical equilibrium to the direction of the formation of the Zn4Si2O7(OH)2H2O salt, resulting in the increase of the selectivity to cyclohexene of the Ru catalyst. When the mass ratio of the Ru catalyst, ZnSO4·7H2O, Na2SiO3·9H2O, diethanolamine and the dispersant ZrO2 was at 1.0:24.6:0.4:0.2:5.0, 2 g of the Ru catalyst will give a selectivity to cyclohexene of 75% and a cyclohexene yield of 55% at a benzene conversion of 73%. Moreover, this catalytic system shows a good reusability and an excellent stability.
2015, 31(7): 1296-1304
doi: 10.11862/CJIC.2015.204
Abstract:
(1-x)Ni0.5Zn0.5Fe2O4-(x)Pb(Zr0.52Ti0.48)O3 (known simply as (1-x)NZFO-(x)PZT, x=0.1, 0.2, 0.3, 0.4, and 0.5) magnetoelectric composite nanofibers have been successfully fabricated using the electrospinning method. The effects of PZT content on structures, electromagnetic characteristics and microwave absorption properties of the resultant products have been investigated in detail. It is found that all the as-prepared composites nanofibers are composed of both spinel-structured NZFO and perovskite-structured PZT phases. The appropriate incorporation of PZT phase in the composite nanofibers can improve the electromagnetic impedance matching and attenuation characteristics of the corresponding microwave absorbing coatings due to the synergistic effects between magnetic loss of NZFO and dielectric loss of PZT and the enhanced interfacial effects, and consequently boost their microwave absorption performances. The (1-x)NZFO-(x)PZT composite nanofiber/silicone microwave absorbing coatings with x=0.3 and 0.4 exhibit the strongest microwave absorption ability in the low- and high-frequency ranges, respectively. When the coating thickness is between 2.5 and 5.0 mm, the minimum reflection loss (RL) value of the x=0.3 sample is -77.2 dB at 6.1 GHz and the effective absorption bandwidth with RL below -10 dB reaches 11.2 GHz covering the 2.8~12.9 and 16.9~18 GHz frequency ranges. While for x=0.4 sample, an optimal RL value of -37.6 dB is observed at 18 GHz and the effective absorption bandwidth is up to 12.5 GHz ranging from 3.3 to 12.5 and 14.7 to 18 GHz.
(1-x)Ni0.5Zn0.5Fe2O4-(x)Pb(Zr0.52Ti0.48)O3 (known simply as (1-x)NZFO-(x)PZT, x=0.1, 0.2, 0.3, 0.4, and 0.5) magnetoelectric composite nanofibers have been successfully fabricated using the electrospinning method. The effects of PZT content on structures, electromagnetic characteristics and microwave absorption properties of the resultant products have been investigated in detail. It is found that all the as-prepared composites nanofibers are composed of both spinel-structured NZFO and perovskite-structured PZT phases. The appropriate incorporation of PZT phase in the composite nanofibers can improve the electromagnetic impedance matching and attenuation characteristics of the corresponding microwave absorbing coatings due to the synergistic effects between magnetic loss of NZFO and dielectric loss of PZT and the enhanced interfacial effects, and consequently boost their microwave absorption performances. The (1-x)NZFO-(x)PZT composite nanofiber/silicone microwave absorbing coatings with x=0.3 and 0.4 exhibit the strongest microwave absorption ability in the low- and high-frequency ranges, respectively. When the coating thickness is between 2.5 and 5.0 mm, the minimum reflection loss (RL) value of the x=0.3 sample is -77.2 dB at 6.1 GHz and the effective absorption bandwidth with RL below -10 dB reaches 11.2 GHz covering the 2.8~12.9 and 16.9~18 GHz frequency ranges. While for x=0.4 sample, an optimal RL value of -37.6 dB is observed at 18 GHz and the effective absorption bandwidth is up to 12.5 GHz ranging from 3.3 to 12.5 and 14.7 to 18 GHz.
2015, 31(7): 1305-1314
doi: 10.11862/CJIC.2015.205
Abstract:
To test the influence of the position and electronic effect of the substituted group on the reaction system, detailed studies on the reactivity of unsaturated 16e half-sandwich complex Cp*Ir(S2C2B10H10) (1) with ortho- and meta-substituted phenyl azides were performed. Reaction of 1 with ortho- and meta-substituted phenyl azides led to the formation of metal complexes in which C-H activation at ortho-position of aryl ring happened to construct a new C-S bond. These complexes were fully characterized by NMR (1H, 11B, 13C), FTIR, MS, elemental analysis and single crystal X-ray diffraction. Basing on the results of the same reaction system with irradiation, the radical mechanism for the formation of these complexes was proposed.
To test the influence of the position and electronic effect of the substituted group on the reaction system, detailed studies on the reactivity of unsaturated 16e half-sandwich complex Cp*Ir(S2C2B10H10) (1) with ortho- and meta-substituted phenyl azides were performed. Reaction of 1 with ortho- and meta-substituted phenyl azides led to the formation of metal complexes in which C-H activation at ortho-position of aryl ring happened to construct a new C-S bond. These complexes were fully characterized by NMR (1H, 11B, 13C), FTIR, MS, elemental analysis and single crystal X-ray diffraction. Basing on the results of the same reaction system with irradiation, the radical mechanism for the formation of these complexes was proposed.
2015, 31(7): 1315-1320
doi: 10.11862/CJIC.2015.199
Abstract:
TiO2 and SiO2 thin films were respectively deposited on K9 glass, monocrystalline silicon and quartz glass substrates by using the sol-gel method. The surface morphology and optical properties of the films were characterized by SEM, UV-Vis and spectroscopic ellipsometer. Among the three substrates, on the monocrystalline silicon substrate TiO2 and SiO2 thin films have the largest refractive index; On the amorphous K9 glass and quartz glass substrate, refractive index and light transmittance of TiO2 film are quite different; On the amorphous substrate, refractive index and light transmittance of SiO2 are similar; SiO2 and TiO2 film have a law that with increased the number of wavelength, the refractive index and extinction coefficient reduced; Cauchy model could describe optical properties of films very on the silicon substrate well in 300~700 nm waveband.
TiO2 and SiO2 thin films were respectively deposited on K9 glass, monocrystalline silicon and quartz glass substrates by using the sol-gel method. The surface morphology and optical properties of the films were characterized by SEM, UV-Vis and spectroscopic ellipsometer. Among the three substrates, on the monocrystalline silicon substrate TiO2 and SiO2 thin films have the largest refractive index; On the amorphous K9 glass and quartz glass substrate, refractive index and light transmittance of TiO2 film are quite different; On the amorphous substrate, refractive index and light transmittance of SiO2 are similar; SiO2 and TiO2 film have a law that with increased the number of wavelength, the refractive index and extinction coefficient reduced; Cauchy model could describe optical properties of films very on the silicon substrate well in 300~700 nm waveband.
2015, 31(7): 1321-1328
doi: 10.11862/CJIC.2015.116
Abstract:
Schiff base organotin complexes 1 and 2 have been synthesized via the reaction of the o-Vanillin-2-amino-4-nitrophenol Schiff base(H2L) with the dibutyltin oxide and the dibenzyltin dichloride, respectively. The complexes have been characterized by IR, 1H NMR, 13C NMR spectra, elemental analysis and the crystal structures have been determined by X-ray diffraction. The anticancer activity of H2L, 1 and 2 against five species of cancer cell which are Hela, MCF7, HepG2, Colo205, NCI-H460 were tested respectively, and the tests showed that complex 1 was more active than carboplatin against tested carcinoma cell lines and has a potential application of drug preparation. The interaction between Schiff base ligand, complex 2 and Herring sperm DNA were studied by EB fluorescent probe, the result shows that fluorescence quenching was really resulted from the synergistic effect of the Schiff base ligand. CCDC: 939077, 1; 939078, 2.
Schiff base organotin complexes 1 and 2 have been synthesized via the reaction of the o-Vanillin-2-amino-4-nitrophenol Schiff base(H2L) with the dibutyltin oxide and the dibenzyltin dichloride, respectively. The complexes have been characterized by IR, 1H NMR, 13C NMR spectra, elemental analysis and the crystal structures have been determined by X-ray diffraction. The anticancer activity of H2L, 1 and 2 against five species of cancer cell which are Hela, MCF7, HepG2, Colo205, NCI-H460 were tested respectively, and the tests showed that complex 1 was more active than carboplatin against tested carcinoma cell lines and has a potential application of drug preparation. The interaction between Schiff base ligand, complex 2 and Herring sperm DNA were studied by EB fluorescent probe, the result shows that fluorescence quenching was really resulted from the synergistic effect of the Schiff base ligand. CCDC: 939077, 1; 939078, 2.
2015, 31(7): 1329-1334
doi: 10.11862/CJIC.2015.191
Abstract:
Hollow silica nanospheres with thiol groups (SiO2-SH NSs) have been successfully prepared through a hydrothermal route. Then the SiO2-SH NSs was further modified by conjugating iminodiacetic acid (IDA) to bear dual chelating groups (-SH and -COOH). After chelating Ni2+, these hollow NSs with dual chelating groups were applied to purify histidine-tagged (His-tagged) proteins. Results show that these hollow NSs can be widely used to separate His-tagged proteins and have a good reused ability.
Hollow silica nanospheres with thiol groups (SiO2-SH NSs) have been successfully prepared through a hydrothermal route. Then the SiO2-SH NSs was further modified by conjugating iminodiacetic acid (IDA) to bear dual chelating groups (-SH and -COOH). After chelating Ni2+, these hollow NSs with dual chelating groups were applied to purify histidine-tagged (His-tagged) proteins. Results show that these hollow NSs can be widely used to separate His-tagged proteins and have a good reused ability.
2015, 31(7): 1335-1341
doi: 10.11862/CJIC.2015.163
Abstract:
LaMnO3, LaFeO3, La0.5Sr0.5MnO3, La0.5Sr0.5FeO3 were prepared by citric acid method and Pt/LaMnO3, Pt/LaFeO3, Pt/La0.5Sr0.5MnO3, Pt/La0.5Sr0.5FeO3 were prepared by impregnating nano-Pt solution to ABO3 mixed oxides. It showed that prepared ABO3 mixed oxides possessed pervoskite structrue from XRD and IR data, the size of nano-Pt particle was about ~3 nm and dispersed uniformly on ABO3 mixed oxides from TEM. It was found that the redox properties determined the catalytic properties of ABO3-type catalsysts in CO catalytic oxidation, thus, Mn-ABO3 catalsysts gave the better activity in CO catalytic oxidation. When supported nano-Pt paricle to ABO3- mixed oxides, Pt/Fe-ABO3 catalsysts showed the excellent activity, the reaction temperature of 100% CO conversion was reduced from 350 ℃ to 120 ℃. Adsorption experiment indicated that oxygen vacancy on ABO3 mixed oxides was a key factor to improve the adsorption of oxygen and to determine the properties of CO oxidation at lower reaction temperatures.
LaMnO3, LaFeO3, La0.5Sr0.5MnO3, La0.5Sr0.5FeO3 were prepared by citric acid method and Pt/LaMnO3, Pt/LaFeO3, Pt/La0.5Sr0.5MnO3, Pt/La0.5Sr0.5FeO3 were prepared by impregnating nano-Pt solution to ABO3 mixed oxides. It showed that prepared ABO3 mixed oxides possessed pervoskite structrue from XRD and IR data, the size of nano-Pt particle was about ~3 nm and dispersed uniformly on ABO3 mixed oxides from TEM. It was found that the redox properties determined the catalytic properties of ABO3-type catalsysts in CO catalytic oxidation, thus, Mn-ABO3 catalsysts gave the better activity in CO catalytic oxidation. When supported nano-Pt paricle to ABO3- mixed oxides, Pt/Fe-ABO3 catalsysts showed the excellent activity, the reaction temperature of 100% CO conversion was reduced from 350 ℃ to 120 ℃. Adsorption experiment indicated that oxygen vacancy on ABO3 mixed oxides was a key factor to improve the adsorption of oxygen and to determine the properties of CO oxidation at lower reaction temperatures.
2015, 31(7): 1342-1350
doi: 10.11862/CJIC.2015.187
Abstract:
Zinc chrome bimetal layered materials (ZnxCr-LDHs, x=2, 3, 4) were successfully synthesized by the coprecipitation method and different factors on the adsorption of AR14 were also investigated. The characterization of XRD, ICP, FTIR and BET revealed that the crystal structures of ZnxCr-LDHs (x=2, 3, 4) were very good and stable, it had the mesoporous structure. Experimental results indicated that the optimum sorbent was Zn3Cr-LDHs with a specific surface area of 101 m2·g-1, the maximum adsorption capacity for AR14 was 484.63 mg·g-1. Moreover, lower pH value and higher temperature were favorable to the removal of AR14. Adsorption isotherms and kinetics showed that the adsorption process could be well fitted with the pseudo-second-order kinetic and Freundlich equation. Based on the analysis of Materials Studio 5.5 simulation, the adsorption menchanism was that AR14 were adsorbed on the surface of Zn3Cr-LDHs, the -SO3- group was the reaction point.
Zinc chrome bimetal layered materials (ZnxCr-LDHs, x=2, 3, 4) were successfully synthesized by the coprecipitation method and different factors on the adsorption of AR14 were also investigated. The characterization of XRD, ICP, FTIR and BET revealed that the crystal structures of ZnxCr-LDHs (x=2, 3, 4) were very good and stable, it had the mesoporous structure. Experimental results indicated that the optimum sorbent was Zn3Cr-LDHs with a specific surface area of 101 m2·g-1, the maximum adsorption capacity for AR14 was 484.63 mg·g-1. Moreover, lower pH value and higher temperature were favorable to the removal of AR14. Adsorption isotherms and kinetics showed that the adsorption process could be well fitted with the pseudo-second-order kinetic and Freundlich equation. Based on the analysis of Materials Studio 5.5 simulation, the adsorption menchanism was that AR14 were adsorbed on the surface of Zn3Cr-LDHs, the -SO3- group was the reaction point.
2015, 31(7): 1351-1356
doi: 10.11862/CJIC.2015.182
Abstract:
Nanostructured greigite (Fe3S4) prepared by hydrothermal method was firstly used as a cathode material for rechargeable magnesium battery. The as-synthesized samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Cyclic voltammetry and galvanostatic charge-discharge cycling tests showed that the obtained Fe3S4 could be reversibly cycled in rechargeable magnesium battery. The discharge voltage plateau located at 0.9 V. The nanostructured Fe3S4 electrode exhibited a high capacity of 267 mAh·g-1 during the first discharge process, then the capacity gradually dropped to 110 mAh·g-1 after 50 cycles. Electrochemical impedance spectroscopy tests showed that Mg2+ can diffuse in the lattice of Fe3S4.
Nanostructured greigite (Fe3S4) prepared by hydrothermal method was firstly used as a cathode material for rechargeable magnesium battery. The as-synthesized samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Cyclic voltammetry and galvanostatic charge-discharge cycling tests showed that the obtained Fe3S4 could be reversibly cycled in rechargeable magnesium battery. The discharge voltage plateau located at 0.9 V. The nanostructured Fe3S4 electrode exhibited a high capacity of 267 mAh·g-1 during the first discharge process, then the capacity gradually dropped to 110 mAh·g-1 after 50 cycles. Electrochemical impedance spectroscopy tests showed that Mg2+ can diffuse in the lattice of Fe3S4.
2015, 31(7): 1357-1364
doi: 10.11862/CJIC.2015.183
Abstract:
Based on the bidentate schiff base ligands involving phenyl and imidazole groups, two homochiral mononuclear spin-crossover iron(Ⅱ) complexes, fac-Δ-[Fe(S-L1)3][ClO4]2 (1), mer-Λ-[Fe(R-L2)3][ClO4]2·Et2O (2) (L1=1-parachlorophenyl-N-(1-n-propylenyl-1H-imidazol-2-ylmethylene)ethanamine; L2=1-phenyl-N-(1-iso-butenyl-1H-imidazol-2-ylmethylene)ethanamine) have been synthesized. The two complexes have been determined by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra, 1H NMR spectra, UV spectra and CD spectra. X-ray crystallography revealed that the iron(Ⅱ) center in 1 and 2 assumed an octahedral coordination environment with 6 N donor atoms from three unsymmetrical bidentate chiral schiff base ligands. Each unit contained one [Fe(Ln)3]2+ cation and two ClO4- anions in 1. While 2 contained two [Fe(Ln)3]2+ cation, four ClO4- anions and one diethyl ether molecular. [Fe(Ln)3]2+ components were chiral with single configuration due to the screw coordination arrangement of the chiral ligand around Fe(Ⅱ) centers. The Fe(Ⅱ)-N bond distances indicated that the Fe(Ⅱ) sites of 1 were in low-spin state, while the Fe(Ⅱ) centers of 2 were in high-spin state. As for [Fe(Ln)3]2+, intramolecular π-π interactions were present between phenyl group and imidazole ring of an adjacent ligand. In 1 and 2, supramolecular architectures were formed through intermolecular C-H…π and/or C-Cl…π interactions. Circular dichromism spectra confirmed the presence of non-racemic chiral metal centers in solution for complexes 1 and 2. Magnetic measurements revealed that 1 and 2 displayed obviously spin-crossover behaviour at 372 K and 146 K, respectively. Complexes 1 and 2 crystallized in different packing modes and intermolecular interactions, therefore their SCO bahaviors were different.
Based on the bidentate schiff base ligands involving phenyl and imidazole groups, two homochiral mononuclear spin-crossover iron(Ⅱ) complexes, fac-Δ-[Fe(S-L1)3][ClO4]2 (1), mer-Λ-[Fe(R-L2)3][ClO4]2·Et2O (2) (L1=1-parachlorophenyl-N-(1-n-propylenyl-1H-imidazol-2-ylmethylene)ethanamine; L2=1-phenyl-N-(1-iso-butenyl-1H-imidazol-2-ylmethylene)ethanamine) have been synthesized. The two complexes have been determined by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra, 1H NMR spectra, UV spectra and CD spectra. X-ray crystallography revealed that the iron(Ⅱ) center in 1 and 2 assumed an octahedral coordination environment with 6 N donor atoms from three unsymmetrical bidentate chiral schiff base ligands. Each unit contained one [Fe(Ln)3]2+ cation and two ClO4- anions in 1. While 2 contained two [Fe(Ln)3]2+ cation, four ClO4- anions and one diethyl ether molecular. [Fe(Ln)3]2+ components were chiral with single configuration due to the screw coordination arrangement of the chiral ligand around Fe(Ⅱ) centers. The Fe(Ⅱ)-N bond distances indicated that the Fe(Ⅱ) sites of 1 were in low-spin state, while the Fe(Ⅱ) centers of 2 were in high-spin state. As for [Fe(Ln)3]2+, intramolecular π-π interactions were present between phenyl group and imidazole ring of an adjacent ligand. In 1 and 2, supramolecular architectures were formed through intermolecular C-H…π and/or C-Cl…π interactions. Circular dichromism spectra confirmed the presence of non-racemic chiral metal centers in solution for complexes 1 and 2. Magnetic measurements revealed that 1 and 2 displayed obviously spin-crossover behaviour at 372 K and 146 K, respectively. Complexes 1 and 2 crystallized in different packing modes and intermolecular interactions, therefore their SCO bahaviors were different.
2015, 31(7): 1365-1372
doi: 10.11862/CJIC.2015.197
Abstract:
Sodium sulfide-selenium prepared by adding Se powder into the Na2S methanol-water solution was used as the anionic precursor, and the methanol-water solution of Cd(NO3)2 and Mn(CH3COO)2 was used as the cationic precursor, respectively. Then, cadmium sulfide-selenium quantum dots sensitized TiO2 photoanodes (CdSSe2/TiO2) and Mn2+ doped cadmium sulfide-selenium quantum dots sensitized TiO2 photoanodes (Mn-CdSSe2/TiO2) were successfully prepared by the successive ionic layer adsorption and reaction (SILAR) for Quantum dots solar cell (QDSC). The Raman spectrum, XPS were applied to analyze the chemical bonds of the Na2SSe2 precursors. EDX and UV-Vis were investigated the composition and light absorption property of Mn-CdSSe2/TiO2 photoanode. J-V curves and IPCE were used to characterize photovoltaic performance of the as-prepared CdS/TiO2, CdSSe2/TiO2 and Mn-CdSSe2/TiO2 photoanodes. The results reveals that the Mn-CdSSe2/TiO2 photoanode with enhanced energy conversion efficiency has been fabricated by SILAR method using the anionic precursors prepared with 0.12 mol·L-1 Se and 0.5 mol·L-1 Na2S, the cationic precursor of 0.5 mol·L-1 Cd2+ and 0.3 mol·L-1 Mn2+. Compared with the CdSSe2/TiO2 and CdS/TiO2 photoanodes, the efficiency of the Mn-CdSSe2/TiO2 photoanode is increased by 90% and 247%, separately.
Sodium sulfide-selenium prepared by adding Se powder into the Na2S methanol-water solution was used as the anionic precursor, and the methanol-water solution of Cd(NO3)2 and Mn(CH3COO)2 was used as the cationic precursor, respectively. Then, cadmium sulfide-selenium quantum dots sensitized TiO2 photoanodes (CdSSe2/TiO2) and Mn2+ doped cadmium sulfide-selenium quantum dots sensitized TiO2 photoanodes (Mn-CdSSe2/TiO2) were successfully prepared by the successive ionic layer adsorption and reaction (SILAR) for Quantum dots solar cell (QDSC). The Raman spectrum, XPS were applied to analyze the chemical bonds of the Na2SSe2 precursors. EDX and UV-Vis were investigated the composition and light absorption property of Mn-CdSSe2/TiO2 photoanode. J-V curves and IPCE were used to characterize photovoltaic performance of the as-prepared CdS/TiO2, CdSSe2/TiO2 and Mn-CdSSe2/TiO2 photoanodes. The results reveals that the Mn-CdSSe2/TiO2 photoanode with enhanced energy conversion efficiency has been fabricated by SILAR method using the anionic precursors prepared with 0.12 mol·L-1 Se and 0.5 mol·L-1 Na2S, the cationic precursor of 0.5 mol·L-1 Cd2+ and 0.3 mol·L-1 Mn2+. Compared with the CdSSe2/TiO2 and CdS/TiO2 photoanodes, the efficiency of the Mn-CdSSe2/TiO2 photoanode is increased by 90% and 247%, separately.
2015, 31(7): 1373-1379
doi: 10.11862/CJIC.2015.181
Abstract:
The two bis[tri(2-methyl-2-phenyl)propyltin]dicarboxylates (CH2)n[CO2Sn(CH2CMe2Ph)3]2 (n=5 (1), 6 (2)) have been synthesized by the reaction of pimelic acid and suberic acid with bis[tri(2-methyl-2-phenyl)propyltin]oxide, respectively. IR, 1H and 13C NMR, elemental analysis and X-ray diffraction for the title complexes were presented. The two complexes belong to monoclinic, space group P21/c. The tin atoms have a distorted tetrahedral geometry. A 1D chain structure of complex 1 is generated by intermolecular hydrogen bonds and a 2D network structure of complex 2 is formed by C-H…O and C-H…π interactions. The thermal gravimetric analysis has showed that the complexes 1 and 2 are stable below 340 ℃. The two complexes showed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, and have antibacterial activity.
The two bis[tri(2-methyl-2-phenyl)propyltin]dicarboxylates (CH2)n[CO2Sn(CH2CMe2Ph)3]2 (n=5 (1), 6 (2)) have been synthesized by the reaction of pimelic acid and suberic acid with bis[tri(2-methyl-2-phenyl)propyltin]oxide, respectively. IR, 1H and 13C NMR, elemental analysis and X-ray diffraction for the title complexes were presented. The two complexes belong to monoclinic, space group P21/c. The tin atoms have a distorted tetrahedral geometry. A 1D chain structure of complex 1 is generated by intermolecular hydrogen bonds and a 2D network structure of complex 2 is formed by C-H…O and C-H…π interactions. The thermal gravimetric analysis has showed that the complexes 1 and 2 are stable below 340 ℃. The two complexes showed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460, and have antibacterial activity.
2015, 31(7): 1380-1386
doi: 10.11862/CJIC.2015.189
Abstract:
The copper(Ⅱ) and nickel(Ⅱ) complexes of nicotinoyl hydrazone Schiff base, [Cu(Py)(HL1)]2 (1) and [Ni(L2)2] (2), where H3L1 is pyridine-3-carboxylic acid (2,4-dihydroxy-benzylidene)hydrazide, HL2 is pyridine-3-carboxylic acid (pyridine-2-yl ethylidyne)hydrazide, were respectively synthesized by slow evaporation methods in mixed-solvent, and characterized by elemental analysis, IR, UV-Vis, FL spectra, TGA and single crystal X-ray diffraction. The crystals of 1 and 2 belongs to the monoclinic system, space group P21/c with cell parameters (1) a=0.739 86(12) nm, b=1.903 7(3) nm, c=1.154 86(19) nm, β=105.090(3)°, V=1.570 5(4) nm3 and (2) a=2.034 0(5) nm, b=1.183 2(3) nm, c=1.020 7(3) nm, V=2.456 1(11) nm3. The complex 1 is a centrosymmetric binuclear complex with Cu(Ⅱ) ions in square pyramidal geometry. The structure units of 1 are linked by intermolecular π-π interactions and O-H…N hydrogen bonds, forming three-dimensional supermolecular network. In 2, the Ni(Ⅱ) ions act as distorted octahedral geometry, being surrounded by two imine nitrogen atoms, two deprotonated amide oxygen atoms and two pyridyl nitrogen atoms from two monovalence anions of HL2 ligand. The tests showed the two complexes displayed good thermal stability below 315 ℃ (1)和358 ℃ (2), respectively.
The copper(Ⅱ) and nickel(Ⅱ) complexes of nicotinoyl hydrazone Schiff base, [Cu(Py)(HL1)]2 (1) and [Ni(L2)2] (2), where H3L1 is pyridine-3-carboxylic acid (2,4-dihydroxy-benzylidene)hydrazide, HL2 is pyridine-3-carboxylic acid (pyridine-2-yl ethylidyne)hydrazide, were respectively synthesized by slow evaporation methods in mixed-solvent, and characterized by elemental analysis, IR, UV-Vis, FL spectra, TGA and single crystal X-ray diffraction. The crystals of 1 and 2 belongs to the monoclinic system, space group P21/c with cell parameters (1) a=0.739 86(12) nm, b=1.903 7(3) nm, c=1.154 86(19) nm, β=105.090(3)°, V=1.570 5(4) nm3 and (2) a=2.034 0(5) nm, b=1.183 2(3) nm, c=1.020 7(3) nm, V=2.456 1(11) nm3. The complex 1 is a centrosymmetric binuclear complex with Cu(Ⅱ) ions in square pyramidal geometry. The structure units of 1 are linked by intermolecular π-π interactions and O-H…N hydrogen bonds, forming three-dimensional supermolecular network. In 2, the Ni(Ⅱ) ions act as distorted octahedral geometry, being surrounded by two imine nitrogen atoms, two deprotonated amide oxygen atoms and two pyridyl nitrogen atoms from two monovalence anions of HL2 ligand. The tests showed the two complexes displayed good thermal stability below 315 ℃ (1)和358 ℃ (2), respectively.
2015, 31(7): 1387-1392
doi: 10.11862/CJIC.2015.201
Abstract:
Two complexes, {[Co(L)(H2O)3]Cl2·2H2O}n(1) and [Cu2(L)2Cl4]·3C2H5OH (2) were synthesized from the reaction of phenanthroline substituted glycoluril (L) with CoCl2·6H2O and CuCl2·2H2O, and characterized by elemental analysis, IR and single crystal X-ray diffraction. Complex 1 crystallized in the orthorhombic system, space group P212121, the coordination environment of Co(Ⅱ) adopted a distorted octahedron geometry, being bound to three oxygen donor from one H2O molecule as well as to two nitrogen atoms and oxygen atoms from two adjacent molecules of L. Each ligand L acted as a tridentate ligand coordinating two metal atoms to generate a one-dimensional(1D) chain structure. Complex 2 crystallized in the monoclinic system, space group P21/n, the coordination environment of Cu(Ⅱ) adopted a distorted square taper geometry, being bound to three chlorine atom as well as to two nitrogen atoms from ligand L. There are two chlorine atoms coordinating two metal atoms to generate binuclear complex 2.
Two complexes, {[Co(L)(H2O)3]Cl2·2H2O}n(1) and [Cu2(L)2Cl4]·3C2H5OH (2) were synthesized from the reaction of phenanthroline substituted glycoluril (L) with CoCl2·6H2O and CuCl2·2H2O, and characterized by elemental analysis, IR and single crystal X-ray diffraction. Complex 1 crystallized in the orthorhombic system, space group P212121, the coordination environment of Co(Ⅱ) adopted a distorted octahedron geometry, being bound to three oxygen donor from one H2O molecule as well as to two nitrogen atoms and oxygen atoms from two adjacent molecules of L. Each ligand L acted as a tridentate ligand coordinating two metal atoms to generate a one-dimensional(1D) chain structure. Complex 2 crystallized in the monoclinic system, space group P21/n, the coordination environment of Cu(Ⅱ) adopted a distorted square taper geometry, being bound to three chlorine atom as well as to two nitrogen atoms from ligand L. There are two chlorine atoms coordinating two metal atoms to generate binuclear complex 2.
2015, 31(7): 1393-1401
doi: 10.11862/CJIC.2015.194
Abstract:
(CO)5MnCOCH3 (1) was synthesized in two steps. A solution 1 with Me2PhSiH in C6D6 was continuously monitored by 1H NMR spectroscopy for 9 h and reaction profile was established using timely contents (mmol) obtained by directly integrating chemical labels of the reactants and derivatives against that of the internal standard C6H5(CH2)2C6H5. 9 intermediates and final products emerged in the extensive hydrosilation were prepared and the molecular structures of the derivations generated in the reaction process were positively confirmed by comparison of their NMR spectra with that of real substances. All besides the 6 species that were quantified by direct integration of their chemical labels the other 3 were indirectly quantified by combination of chemical stoichiometry and integration of their chemical labels. Attempt was made to make plausible explanations for the origins of these species. Finally, a mechanism with multiple step reactions process and double pathways was proposed. More than 90.7% of the total manganese source was accounted for at 9 h and meanwhile that of more than 91.4% of the total silicon source was accounted for.
(CO)5MnCOCH3 (1) was synthesized in two steps. A solution 1 with Me2PhSiH in C6D6 was continuously monitored by 1H NMR spectroscopy for 9 h and reaction profile was established using timely contents (mmol) obtained by directly integrating chemical labels of the reactants and derivatives against that of the internal standard C6H5(CH2)2C6H5. 9 intermediates and final products emerged in the extensive hydrosilation were prepared and the molecular structures of the derivations generated in the reaction process were positively confirmed by comparison of their NMR spectra with that of real substances. All besides the 6 species that were quantified by direct integration of their chemical labels the other 3 were indirectly quantified by combination of chemical stoichiometry and integration of their chemical labels. Attempt was made to make plausible explanations for the origins of these species. Finally, a mechanism with multiple step reactions process and double pathways was proposed. More than 90.7% of the total manganese source was accounted for at 9 h and meanwhile that of more than 91.4% of the total silicon source was accounted for.
2015, 31(7): 1402-1408
doi: 10.11862/CJIC.2015.166
Abstract:
Two cobalt(Ⅱ) complexes, Co2(MBimB)2Cl4·2H2O·EDA (1) (MBimb=1,3-bis(2-benzimidazolyl)benzene, EDa=ethylenediamine) and [Co(MBimB)Cl2]n (2), have been synthesized based on the rigid ligand MBimB and characterized by single crystal X-ray diffraction. In complex 1, two MBimB molecules adopt "cis" conformation and bridge two cobalt(Ⅱ) ions to form a binuclear metallaycyclic framework. In complex 2, MBimB ligand adopts "trans" conformation and bridges two adjacent cobalt(Ⅱ) ions into 1D zigzag chain. Magnetic susceptibility of 1 and 2 showed ferromagnetic coupling firstly and then antiferromagnetic coupling as the temperature decreases. Compared to complex 2, stronger ferromagnetic interaction and/or spin-orbital coupling between the cobalt(Ⅱ) ions in 1 can be ascribed to the shorter distance of Co…Co and enhanced intervening aromatic π-system between the metal centers.
Two cobalt(Ⅱ) complexes, Co2(MBimB)2Cl4·2H2O·EDA (1) (MBimb=1,3-bis(2-benzimidazolyl)benzene, EDa=ethylenediamine) and [Co(MBimB)Cl2]n (2), have been synthesized based on the rigid ligand MBimB and characterized by single crystal X-ray diffraction. In complex 1, two MBimB molecules adopt "cis" conformation and bridge two cobalt(Ⅱ) ions to form a binuclear metallaycyclic framework. In complex 2, MBimB ligand adopts "trans" conformation and bridges two adjacent cobalt(Ⅱ) ions into 1D zigzag chain. Magnetic susceptibility of 1 and 2 showed ferromagnetic coupling firstly and then antiferromagnetic coupling as the temperature decreases. Compared to complex 2, stronger ferromagnetic interaction and/or spin-orbital coupling between the cobalt(Ⅱ) ions in 1 can be ascribed to the shorter distance of Co…Co and enhanced intervening aromatic π-system between the metal centers.
2015, 31(7): 1409-1416
doi: 10.11862/CJIC.2015.193
Abstract:
One monomeric complex [Mn(HMPCA)2(phen)]·2H2O (1) and one 1D coordination polymer [Cd2(HMPCA)2 (phen)2(H2O)2]·2H2O (2) with binuclear structural unit (H2MPCa=5-methyl-1H-pyrazole-3-carboxylic acid, phen=phenanthroline) have been synthesized and characterized by elemental analysis, IR spectra, thermogravimetric analysis and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic system, space group P1, while 2 in the orthorhombic system, space group Pccn. In 1, Mn(Ⅱ) ion located in a distorted octahedral coordination geometry, discrete water molecules and mononucleate units are assembled into a 3D supramolecular network. In 2, each Cd(Ⅱ) ion located in a pentagonal bipyramid geometry. Each carboxyl group from HMPA- anion bridges two adjacent Cd(Ⅱ) ions, forming a 1D chain. These chains and water molecules are connected by hydrogen bonds, forming a 3D supramolecular framework. The thermal stability and luminescent properties of them are also investigated. CCDC: 1044243, 1; 1044244, 2.
One monomeric complex [Mn(HMPCA)2(phen)]·2H2O (1) and one 1D coordination polymer [Cd2(HMPCA)2 (phen)2(H2O)2]·2H2O (2) with binuclear structural unit (H2MPCa=5-methyl-1H-pyrazole-3-carboxylic acid, phen=phenanthroline) have been synthesized and characterized by elemental analysis, IR spectra, thermogravimetric analysis and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic system, space group P1, while 2 in the orthorhombic system, space group Pccn. In 1, Mn(Ⅱ) ion located in a distorted octahedral coordination geometry, discrete water molecules and mononucleate units are assembled into a 3D supramolecular network. In 2, each Cd(Ⅱ) ion located in a pentagonal bipyramid geometry. Each carboxyl group from HMPA- anion bridges two adjacent Cd(Ⅱ) ions, forming a 1D chain. These chains and water molecules are connected by hydrogen bonds, forming a 3D supramolecular framework. The thermal stability and luminescent properties of them are also investigated. CCDC: 1044243, 1; 1044244, 2.
2015, 31(7): 1417-1424
doi: 10.11862/CJIC.2015.184
Abstract:
Two copper phosphonates [Cu3(L)2(bpy)2(H2O)2]·2H2O (1) and [Cu3(L)2(bpy)2(H2O)3]·2H2O (2) (H3L=6-hydroxy-2-pyridinephosphonic acid, bpy=4,4'-bipyridine, bpe=trans-1,2-bis(4-pyridyl)ethylene) were synthesized under hydrothermal conditions. In compound 1 the Cu2+ ions are bridged by the phosphonate ligand into one chain, which are further bridged by bpy into a 2D layer. The layers are interlinked by hydrogen bonds into 3D supramolecular network. Compound 2 is isostructural to compound 1, however, the bridge ligand is bpe. Magnetic measurements indicate antiferromagnetic interactions are propagated among the Cu2+ centers in compound 1 and 2.
Two copper phosphonates [Cu3(L)2(bpy)2(H2O)2]·2H2O (1) and [Cu3(L)2(bpy)2(H2O)3]·2H2O (2) (H3L=6-hydroxy-2-pyridinephosphonic acid, bpy=4,4'-bipyridine, bpe=trans-1,2-bis(4-pyridyl)ethylene) were synthesized under hydrothermal conditions. In compound 1 the Cu2+ ions are bridged by the phosphonate ligand into one chain, which are further bridged by bpy into a 2D layer. The layers are interlinked by hydrogen bonds into 3D supramolecular network. Compound 2 is isostructural to compound 1, however, the bridge ligand is bpe. Magnetic measurements indicate antiferromagnetic interactions are propagated among the Cu2+ centers in compound 1 and 2.
2015, 31(7): 1425-1432
doi: 10.11862/CJIC.2015.176
Abstract:
Two lanthanide complexes [Ln(3,4-DFBA)3(phen)(H2O)]2(H2O)2 (Ln=Sm (1), Ho (2); 3,4-DFBa=3,4-difluorobenzoate, phen=1,10-phenanthroline) were prepared by hydrothermal method. Their structures were determined by single-crystal X-ray diffraction method. The structures of complexes 1 and 2 are isostructural with the coordination number of eight. They crystallized in the triclinic space group P1. The 2D layered structure is formed by intermolecular forces of adjacent two binuclear molecules. The title complexes were characterized by elemental analysis, IR, UV, XRD, and so on. The thermal stability of the complexes was tested using TG-DTG technology. The luminescent property of complex 1 had been explored. Besides, the bacteriostatic activities of the two complexes to candida albicans, Gram negative bacteria (escherichia coli) and Gram positive bacteria (staphylococcus aureus) were also studied.
Two lanthanide complexes [Ln(3,4-DFBA)3(phen)(H2O)]2(H2O)2 (Ln=Sm (1), Ho (2); 3,4-DFBa=3,4-difluorobenzoate, phen=1,10-phenanthroline) were prepared by hydrothermal method. Their structures were determined by single-crystal X-ray diffraction method. The structures of complexes 1 and 2 are isostructural with the coordination number of eight. They crystallized in the triclinic space group P1. The 2D layered structure is formed by intermolecular forces of adjacent two binuclear molecules. The title complexes were characterized by elemental analysis, IR, UV, XRD, and so on. The thermal stability of the complexes was tested using TG-DTG technology. The luminescent property of complex 1 had been explored. Besides, the bacteriostatic activities of the two complexes to candida albicans, Gram negative bacteria (escherichia coli) and Gram positive bacteria (staphylococcus aureus) were also studied.
2015, 31(7): 1433-1438
doi: 10.11862/CJIC.2015.203
Abstract:
The reaction of diamido ligand [K2(L)(THF)2] (1) (L=[Ph2Si(NAr)2]2-, Ar=2,6-iPr2C6H3) with YbI2(THF)2 afforded two complexes [Yb(L)(THF)3] (2) and {Yb(L)2[K(THF)2]2} (3), which were characterized by X-ray structure analysis, NMR and elemental analysis. The coordination geometry of complex 2 is five-coordinated, and Yb metal center is coordinated by one amido ligand and three THF molecules. Complex 3 adopts a four-coordinated, nearly planar geometry around the Yb(Ⅱ) center. Two potassium ion is sandwiched between two phenyl rings via cation-arene π-interactions, which helps to stabilize the metal center.
The reaction of diamido ligand [K2(L)(THF)2] (1) (L=[Ph2Si(NAr)2]2-, Ar=2,6-iPr2C6H3) with YbI2(THF)2 afforded two complexes [Yb(L)(THF)3] (2) and {Yb(L)2[K(THF)2]2} (3), which were characterized by X-ray structure analysis, NMR and elemental analysis. The coordination geometry of complex 2 is five-coordinated, and Yb metal center is coordinated by one amido ligand and three THF molecules. Complex 3 adopts a four-coordinated, nearly planar geometry around the Yb(Ⅱ) center. Two potassium ion is sandwiched between two phenyl rings via cation-arene π-interactions, which helps to stabilize the metal center.
2015, 31(7): 1439-1446
doi: 10.11862/CJIC.2015.202
Abstract:
Two coordination polymers {[Zn(3-Nbdc)(bpmp)]·H2O}n (1) and {[Co(3-Nbdc)(bpmp)(H2O)]·H2O}n (2) (3-Nbdc2-=3-nitrobenzene-1,2-dicarboxylate, bpmp=1,4-bis(4-pyridylmethyl)piperazine) were synthesized hydrother-mally and characterized structurally by single-crystal X-ray diffractions, elemental analysis and infrared spectros-copy (IR). Both complexes 1 and 2 display (4,4) grid layers containing the dinuclear units in 1 and helix metal-carboxylate chains in 2. Thermogravimetric Analyses (TGA), powder X-ray diffractions (PXRD), fluorescence property and magnetic property for compounds 1 and 2 are also investigated. The solid state fluorescence indicates that the complex 1 shows similar emission spectra to the free 3-NbdcH2 ligand due to little contribution from the Zn-O inorganic motifs to the emission and very little degree change of interligand coupling upon metal coordination. The complex 2 exhibits a ferromagnetic coupling between the metal centers in the low-temperature region, and the decrease of χMT value in the high-temperature region may be attributed to the strong spin-orbit coupling through the 4T1g state of the octahedral Co2+ centers.
Two coordination polymers {[Zn(3-Nbdc)(bpmp)]·H2O}n (1) and {[Co(3-Nbdc)(bpmp)(H2O)]·H2O}n (2) (3-Nbdc2-=3-nitrobenzene-1,2-dicarboxylate, bpmp=1,4-bis(4-pyridylmethyl)piperazine) were synthesized hydrother-mally and characterized structurally by single-crystal X-ray diffractions, elemental analysis and infrared spectros-copy (IR). Both complexes 1 and 2 display (4,4) grid layers containing the dinuclear units in 1 and helix metal-carboxylate chains in 2. Thermogravimetric Analyses (TGA), powder X-ray diffractions (PXRD), fluorescence property and magnetic property for compounds 1 and 2 are also investigated. The solid state fluorescence indicates that the complex 1 shows similar emission spectra to the free 3-NbdcH2 ligand due to little contribution from the Zn-O inorganic motifs to the emission and very little degree change of interligand coupling upon metal coordination. The complex 2 exhibits a ferromagnetic coupling between the metal centers in the low-temperature region, and the decrease of χMT value in the high-temperature region may be attributed to the strong spin-orbit coupling through the 4T1g state of the octahedral Co2+ centers.
2015, 31(7): 1447-1452
doi: 10.11862/CJIC.2015.200
Abstract:
Half-sandwich 16e complex CpCoS2C2B10H10 (Cp: cyclopentadienyl) (1) reacted with HC≡CCO2Me in the presence of 2-methylpropanedithioic acid to generate compounds {(C5H4CoS2C2B9H9)(CH=CHCO2Me)(Me2C=CS2H)} (2) and (Me2C=CS2H)3Co (3). In 2, one S-Co bond of 1 was broken, and the S atom linked with the terminal acetylenyl carbon atom of the HC≡CCO2Me. Meanwhile, the Co atom in 1 linked to the S atom in 2-methylpropanedithioic acid with covalent bond while linked to the SH unit with coordinative bond. One carbon atom of Cp ring linked to the B(3)/B(6) cite of the carborane cage. The H atom of the B(3)/B(6) cite migrated to the internal acetylenyl carbon atom to form a trans-ethylenic bond. The Co atom of 1 linked to three S atoms of three 2-methylpropanedithioic acid molecules with covalent bond, while linked to the other three SH units with coordinative bond. As a result, product 3 formed. Complexes 2 and 3 have been characterized by IR, NMR, elemental analysis, mass spectrum and single-crystal X-ray diffraction analysis.
Half-sandwich 16e complex CpCoS2C2B10H10 (Cp: cyclopentadienyl) (1) reacted with HC≡CCO2Me in the presence of 2-methylpropanedithioic acid to generate compounds {(C5H4CoS2C2B9H9)(CH=CHCO2Me)(Me2C=CS2H)} (2) and (Me2C=CS2H)3Co (3). In 2, one S-Co bond of 1 was broken, and the S atom linked with the terminal acetylenyl carbon atom of the HC≡CCO2Me. Meanwhile, the Co atom in 1 linked to the S atom in 2-methylpropanedithioic acid with covalent bond while linked to the SH unit with coordinative bond. One carbon atom of Cp ring linked to the B(3)/B(6) cite of the carborane cage. The H atom of the B(3)/B(6) cite migrated to the internal acetylenyl carbon atom to form a trans-ethylenic bond. The Co atom of 1 linked to three S atoms of three 2-methylpropanedithioic acid molecules with covalent bond, while linked to the other three SH units with coordinative bond. As a result, product 3 formed. Complexes 2 and 3 have been characterized by IR, NMR, elemental analysis, mass spectrum and single-crystal X-ray diffraction analysis.
2015, 31(7): 1453-1459
doi: 10.11862/CJIC.2015.188
Abstract:
Two interesting copper(Ⅱ) complexes,[Cu(H2L)2(THF)] (1) and[Cu2(L)Cl(CH3OH)]·H2O (2) based on H3L {ethyl 5-[(2-hydroxyl-4-methylbenzoyl)amino-iminomethyl]-3,4-dimethyl-pyrrole-2-carboxylate} were synthesized and characterized by X-ray diffraction analyses. The results show that in complex 1, the copper(Ⅱ) ion is surrounded by two mono-deprotonated acylhydrazone ligands with NO donor sets and one THF molecule, and thus possesses a distorted square pyramidal geometry. However, in binuclear complex 2, the acylhydrazone ligand is tri-deprotonated and bridges two copper(Ⅱ) ions with square-planar coordination geometry through NO and N2O2 atom sets, respectively. Both complexes have excellent antitumor activities towards A549, ECA109 and SGC7901 cancer cells.
Two interesting copper(Ⅱ) complexes,[Cu(H2L)2(THF)] (1) and[Cu2(L)Cl(CH3OH)]·H2O (2) based on H3L {ethyl 5-[(2-hydroxyl-4-methylbenzoyl)amino-iminomethyl]-3,4-dimethyl-pyrrole-2-carboxylate} were synthesized and characterized by X-ray diffraction analyses. The results show that in complex 1, the copper(Ⅱ) ion is surrounded by two mono-deprotonated acylhydrazone ligands with NO donor sets and one THF molecule, and thus possesses a distorted square pyramidal geometry. However, in binuclear complex 2, the acylhydrazone ligand is tri-deprotonated and bridges two copper(Ⅱ) ions with square-planar coordination geometry through NO and N2O2 atom sets, respectively. Both complexes have excellent antitumor activities towards A549, ECA109 and SGC7901 cancer cells.
2015, 31(7): 1460-1466
doi: 10.11862/CJIC.2015.177
Abstract:
Two cyanide bridged FeⅢMnⅡ double zigzag chains {[Fe(Tp)(CN)3]2[Mn(bib)]}·CH3OH·2H2O (1) and {[Fe(pzTp)(CN)3]2[Mn(bib)]}·3H2O (2) were synthesized utilizing tricyanometallate building blocks. The chains were further linked via long ditopic ligand to form two dimensional compounds. With the alignment of chains fixed by the rigid ditopic linker, the intrachain magnetic interactions between FeⅢ and MnⅡ could be further tuned via changing the capping ligand of FeⅢ ions.
Two cyanide bridged FeⅢMnⅡ double zigzag chains {[Fe(Tp)(CN)3]2[Mn(bib)]}·CH3OH·2H2O (1) and {[Fe(pzTp)(CN)3]2[Mn(bib)]}·3H2O (2) were synthesized utilizing tricyanometallate building blocks. The chains were further linked via long ditopic ligand to form two dimensional compounds. With the alignment of chains fixed by the rigid ditopic linker, the intrachain magnetic interactions between FeⅢ and MnⅡ could be further tuned via changing the capping ligand of FeⅢ ions.
