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2015 Volume 31 Issue 9
2015, 31(9): 1761-1773
doi: 10.11862/CJIC.2015.190
Abstract:
Bulky inorganic polyhedral oligomeric silsesquioxanes (POSS) moieties were introduced onto the porphyrin periphery in mixed (phthalocyaninato) (porphyrinato) terbium molecule, giving POSS-involved hybrid triple-decker complex Tb2(Pc)[T(OPOSS)4PP]2 (1) [H2Pc=phthalocyanine; H2T(OPOSS)4PP=5, 10, 15, 20-tetra{[[N-[heptakis(isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]. For comparative study, triple-decker analogue Tb2(Pc)(TPP)2 (2) (H2TPP=5, 10, 15, 20-tetraphenyporphyrin) was also prepared and structurally characterized. In particular, Tb2(Pc)[T(OPOSS)4PP]2 (1) and Tb2(Pc)(TPP)2 (2) were revealed to display intrinsic single molecule magnet (SMM) and non-SMM (or field-induced) characteristic, respectively, at zero Oe (or a 3.0 Oe ac field), clearly indicating the effect of the covalently linked, homogenously dispersed POSS moieties on effectively separating the magnetic cores and improving the magnetic property of triple-decker compounds.
Bulky inorganic polyhedral oligomeric silsesquioxanes (POSS) moieties were introduced onto the porphyrin periphery in mixed (phthalocyaninato) (porphyrinato) terbium molecule, giving POSS-involved hybrid triple-decker complex Tb2(Pc)[T(OPOSS)4PP]2 (1) [H2Pc=phthalocyanine; H2T(OPOSS)4PP=5, 10, 15, 20-tetra{[[N-[heptakis(isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]. For comparative study, triple-decker analogue Tb2(Pc)(TPP)2 (2) (H2TPP=5, 10, 15, 20-tetraphenyporphyrin) was also prepared and structurally characterized. In particular, Tb2(Pc)[T(OPOSS)4PP]2 (1) and Tb2(Pc)(TPP)2 (2) were revealed to display intrinsic single molecule magnet (SMM) and non-SMM (or field-induced) characteristic, respectively, at zero Oe (or a 3.0 Oe ac field), clearly indicating the effect of the covalently linked, homogenously dispersed POSS moieties on effectively separating the magnetic cores and improving the magnetic property of triple-decker compounds.
2015, 31(9): 1774-1784
doi: 10.11862/CJIC.2015.245
Abstract:
The speciation of uranium and effect of major fission products after low-enriched uranium targets being irradiated and solvated were analyzed using the geochemical program CHEMSPEC. The results indicate that the speciation of uranium in water is determined by pH value and the concentration of uranyl, and polynuclear complexes may be generated at high concentration of uranyl. Nitrate anion in the solution may interact with uranyl, and at high concentration of nitrate, uranyl exists as UO22+ and UO2NO3+. The presence of CO2 at low concentrations of uranium brings substantial distribution uranyl carbonate, while this is negligible at high concentration of uranyl due to heavy hydrolysis and aggregation of uranyl. The calculations also show that the major fission products, Tc, I, and Mo, do not affect the speciation of uranium when their concentrations are below 0.01 mol·L-1 and when they exist as TcO4-, I-, MoO42-.
The speciation of uranium and effect of major fission products after low-enriched uranium targets being irradiated and solvated were analyzed using the geochemical program CHEMSPEC. The results indicate that the speciation of uranium in water is determined by pH value and the concentration of uranyl, and polynuclear complexes may be generated at high concentration of uranyl. Nitrate anion in the solution may interact with uranyl, and at high concentration of nitrate, uranyl exists as UO22+ and UO2NO3+. The presence of CO2 at low concentrations of uranium brings substantial distribution uranyl carbonate, while this is negligible at high concentration of uranyl due to heavy hydrolysis and aggregation of uranyl. The calculations also show that the major fission products, Tc, I, and Mo, do not affect the speciation of uranium when their concentrations are below 0.01 mol·L-1 and when they exist as TcO4-, I-, MoO42-.
2015, 31(9): 1785-1797
doi: 10.11862/CJIC.2015.249
Abstract:
By using environmentally friendly K2[Ni(CN)4] that slowly hydrolyse upon hydrothermal treatment, cis-[Ni(CN)2(H2O)4] units and cyanides were generated and further assembled with Cu(Ⅰ) atoms into pentagonal heterometallic ribbons. Subsequently, these pentagonal ribbons are induced aggregation via cuprophilic interactions into 2D supramolecular coloured polymorphs [(CuCN)2Ni(CN)2(H2O)4] (1 and 2). Dark blue 1 synthesized at a lower temperature is a denser phase while purple 2 synthesized at a higher temperature is a looser phase, which is abnormal to general rule that a higher reaction time and pressure tends to form a denser phase. Careful examination on structures reveals that slight size difference in pentagons and different interlayer distances of 2D supramolecular arrangement contribute to the abnormality. Besides, the titled compounds could be rare cuprophilicity drived examples of coloured polymorphs, which exhibit remarkable colour difference from dark-blue to purple. Magnetic measurements confirmed that diamagnetic Ni(Ⅱ) atom in square planar [Ni(CN)4]2- is transformed into octahedral coordinated Ni(Ⅱ) with ground state spin S=1.
By using environmentally friendly K2[Ni(CN)4] that slowly hydrolyse upon hydrothermal treatment, cis-[Ni(CN)2(H2O)4] units and cyanides were generated and further assembled with Cu(Ⅰ) atoms into pentagonal heterometallic ribbons. Subsequently, these pentagonal ribbons are induced aggregation via cuprophilic interactions into 2D supramolecular coloured polymorphs [(CuCN)2Ni(CN)2(H2O)4] (1 and 2). Dark blue 1 synthesized at a lower temperature is a denser phase while purple 2 synthesized at a higher temperature is a looser phase, which is abnormal to general rule that a higher reaction time and pressure tends to form a denser phase. Careful examination on structures reveals that slight size difference in pentagons and different interlayer distances of 2D supramolecular arrangement contribute to the abnormality. Besides, the titled compounds could be rare cuprophilicity drived examples of coloured polymorphs, which exhibit remarkable colour difference from dark-blue to purple. Magnetic measurements confirmed that diamagnetic Ni(Ⅱ) atom in square planar [Ni(CN)4]2- is transformed into octahedral coordinated Ni(Ⅱ) with ground state spin S=1.
2015, 31(9): 1798-1804
doi: 10.11862/CJIC.2015.219
Abstract:
Two polynuclear copper complexes containing the flexible ligand N, N'-dimethyl-N, N'-(2-hydroxy-4, 5-dimethylbenzyl)ethylenediamine (H2L) have been prepared and characterized structurally and magnetically. The complexes have the formula [Cu3II(L)2(CH3OH)2](ClO4)2(1) and [Cu3II(L)2(CuICl2)2](2). X-ray single-crystal structure analyses show that both complexes contain linear CuII-CuII-CuII cores where adjacent Cu(Ⅱ) ions are doubly bridged by phenolate groups of L2-. The coordination sphere of the terminal Cu(Ⅱ) ions is square pyramidal with the methanol oxygen (complex 1) or the chloride ion of [CuCl2]- (complex 2) situated at the apical position, whereas the central Cu(Ⅱ) has a square coordination environment. The CuII-O-CuII bridging bond angles are in the range of 100.14°~101.79°. Magnetic studies show that both complexes exhibit strong antiferromagnetic interaction with the spin exchange coupling constants (J) of -277(9) cm-1 (1) and -299(3) cm-1 (2) (Ĥ=-2J(Ŝ1·Ŝ2+Ŝ2·Ŝ3). The antiferromagnetic interactions have been found to be mainly related to the CuII-O-CuII bond angles. Larger Cu-O-Cu bond angles correspond to stronger antiferromagnetic interaction (more negative J values).
Two polynuclear copper complexes containing the flexible ligand N, N'-dimethyl-N, N'-(2-hydroxy-4, 5-dimethylbenzyl)ethylenediamine (H2L) have been prepared and characterized structurally and magnetically. The complexes have the formula [Cu3II(L)2(CH3OH)2](ClO4)2(1) and [Cu3II(L)2(CuICl2)2](2). X-ray single-crystal structure analyses show that both complexes contain linear CuII-CuII-CuII cores where adjacent Cu(Ⅱ) ions are doubly bridged by phenolate groups of L2-. The coordination sphere of the terminal Cu(Ⅱ) ions is square pyramidal with the methanol oxygen (complex 1) or the chloride ion of [CuCl2]- (complex 2) situated at the apical position, whereas the central Cu(Ⅱ) has a square coordination environment. The CuII-O-CuII bridging bond angles are in the range of 100.14°~101.79°. Magnetic studies show that both complexes exhibit strong antiferromagnetic interaction with the spin exchange coupling constants (J) of -277(9) cm-1 (1) and -299(3) cm-1 (2) (Ĥ=-2J(Ŝ1·Ŝ2+Ŝ2·Ŝ3). The antiferromagnetic interactions have been found to be mainly related to the CuII-O-CuII bond angles. Larger Cu-O-Cu bond angles correspond to stronger antiferromagnetic interaction (more negative J values).
2015, 31(9): 1805-1810
doi: 10.11862/CJIC.2015.237
Abstract:
Reactions of the preformed cluster precursors [Et4N]4[MS4Cu4I6] (M=Mo (1a); W (1b)) with a ditopic bridging ligand 1, 2-bis(4-pyridyl)ethane (bpe) in aniline solutions gave rise to two analogous one-dimensional cluster-supported coordination polymers {[MS4Cu4(bpe)2(ani)2I2]·3.5ani}n (M=Mo (2), W (3); ani=aniline). Both 2 and 3 are characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. X-ray analyses revealed that the pentanuclear saddle-shaped [MS4Cu4] cores in 1a and 1b are retained in 2 and 3. The adjacent [MS4Cu4] cores are interconnected by double bpe bridges to afford one-dimensional zigzag chains extending along the [111] direction.
Reactions of the preformed cluster precursors [Et4N]4[MS4Cu4I6] (M=Mo (1a); W (1b)) with a ditopic bridging ligand 1, 2-bis(4-pyridyl)ethane (bpe) in aniline solutions gave rise to two analogous one-dimensional cluster-supported coordination polymers {[MS4Cu4(bpe)2(ani)2I2]·3.5ani}n (M=Mo (2), W (3); ani=aniline). Both 2 and 3 are characterized by elemental analysis, IR spectra, and single crystal X-ray diffraction. X-ray analyses revealed that the pentanuclear saddle-shaped [MS4Cu4] cores in 1a and 1b are retained in 2 and 3. The adjacent [MS4Cu4] cores are interconnected by double bpe bridges to afford one-dimensional zigzag chains extending along the [111] direction.
2015, 31(9): 1811-1819
doi: 10.11862/CJIC.2015.244
Abstract:
2, 6-Pyridine diformylhydrazine 2-hydroxylnaphthene carboxylic hydrazone (L1) was synthesized by acylation, esterification and aminolysis reaction. The effect of pH value on isomerization of L1 and the binding among L1, Cu(Ⅱ) and copper trafficking protein, apoCopC, were studied by using UV-Vis absorption, fluorescence spectra and fluorescence lifetime measurement. The results show that the binding constant is 3.32×106 mol-1·L for Cu(Ⅱ)-L1, 4.01×105 mol-1·L for L1-apoCopC, separately, in pH value of 7.4, 50 mmol·L-1 Tris-HCl. Meanwhile, the binding constant between Cu(Ⅱ)-L1 and apoCopC is 8.09×105 mol-1·L. The average distance between the bound L1 and Trp83 of apoCopC from fluorescence resonance energy transfer was determined and the binding site of L1 in apoCopC, which locats at N-terminal, was shown by an automated public domain software package ArgusLab 4.0.1. The formation of a ternary complex, L1-Cu(Ⅱ)-CopC, is confirmed by the titration of Cu(Ⅱ) to L1-apoCopC in pH value of 7.4 and 50 mmol·L-1 Tris-HCl.
2, 6-Pyridine diformylhydrazine 2-hydroxylnaphthene carboxylic hydrazone (L1) was synthesized by acylation, esterification and aminolysis reaction. The effect of pH value on isomerization of L1 and the binding among L1, Cu(Ⅱ) and copper trafficking protein, apoCopC, were studied by using UV-Vis absorption, fluorescence spectra and fluorescence lifetime measurement. The results show that the binding constant is 3.32×106 mol-1·L for Cu(Ⅱ)-L1, 4.01×105 mol-1·L for L1-apoCopC, separately, in pH value of 7.4, 50 mmol·L-1 Tris-HCl. Meanwhile, the binding constant between Cu(Ⅱ)-L1 and apoCopC is 8.09×105 mol-1·L. The average distance between the bound L1 and Trp83 of apoCopC from fluorescence resonance energy transfer was determined and the binding site of L1 in apoCopC, which locats at N-terminal, was shown by an automated public domain software package ArgusLab 4.0.1. The formation of a ternary complex, L1-Cu(Ⅱ)-CopC, is confirmed by the titration of Cu(Ⅱ) to L1-apoCopC in pH value of 7.4 and 50 mmol·L-1 Tris-HCl.
2015, 31(9): 1820-1826
doi: 10.11862/CJIC.2015.246
Abstract:
Four Keggin-based nanomaterials (PMo12b, PW12b, SiW12b and GeW12b) were controllably prepared. The structure and the size of all the compounds have been characterized by IR, UV-Vis, XRD and SEM. Further investigations showed that four Keggin-based nanomaterials exhibited fast adsorption rate towards dye molecules. The adsorption efficiency of those compounds (100 mg) towards MB (100 mL of 20 mg·L-1) could reach up to 96.3% in the initial 5 min under dark condition, the adsorption efficiency sequence is PMo12b > PW12b > GeW12b > SiW12b. And also, the adsorption efficiency towards RhB (100 mL of 20 mg·L-1)could reach up to 96.1% in 30 min under same conditions, the adsorption efficiency sequence is PW12b > PMo12b > SiW12b > GeW12b. All the investigations indicate that the four kind of POMs-nanomaterials present excellent adsorption properties of the organic dyes.
Four Keggin-based nanomaterials (PMo12b, PW12b, SiW12b and GeW12b) were controllably prepared. The structure and the size of all the compounds have been characterized by IR, UV-Vis, XRD and SEM. Further investigations showed that four Keggin-based nanomaterials exhibited fast adsorption rate towards dye molecules. The adsorption efficiency of those compounds (100 mg) towards MB (100 mL of 20 mg·L-1) could reach up to 96.3% in the initial 5 min under dark condition, the adsorption efficiency sequence is PMo12b > PW12b > GeW12b > SiW12b. And also, the adsorption efficiency towards RhB (100 mL of 20 mg·L-1)could reach up to 96.1% in 30 min under same conditions, the adsorption efficiency sequence is PW12b > PMo12b > SiW12b > GeW12b. All the investigations indicate that the four kind of POMs-nanomaterials present excellent adsorption properties of the organic dyes.
2015, 31(9): 1827-1830
doi: 10.11862/CJIC.2015.250
Abstract:
LiNi0.5Co0.4Al0.1O2 compositions were synthesized by high temperature solid-state method. The crystal structures and surface morphology of LiNi0.5Co0.4Al0.1O2 powders were characterized by X-ray diffractometry(XRD), fourier transform infrared spectrometer(FTIR) and scanning electron microscopy(SEM). The electrochemical properties of LiNi0.5Co0.4Al0.1O2 were examined by charge-discharge tests and cyclic voltammetry. The results showed that thematerial delivered the initial discharge capacity of 159.9 mAh·g-1 with the voltage range 3~4.5 V and 0.2C rate, and it retained 142.6 mAh·g-1 discharge capacity after 50 cycles.
LiNi0.5Co0.4Al0.1O2 compositions were synthesized by high temperature solid-state method. The crystal structures and surface morphology of LiNi0.5Co0.4Al0.1O2 powders were characterized by X-ray diffractometry(XRD), fourier transform infrared spectrometer(FTIR) and scanning electron microscopy(SEM). The electrochemical properties of LiNi0.5Co0.4Al0.1O2 were examined by charge-discharge tests and cyclic voltammetry. The results showed that thematerial delivered the initial discharge capacity of 159.9 mAh·g-1 with the voltage range 3~4.5 V and 0.2C rate, and it retained 142.6 mAh·g-1 discharge capacity after 50 cycles.
2015, 31(9): 1831-1838
doi: 10.11862/CJIC.2015.260
Abstract:
A multidentate salicylaldehyde Schiff-base ligand with {NO4} donor set, 3, 5-di-tert-butylsalicylaldehyde-trihydroxymethylaminomethane (H4L), has been synthesized for the first time and characterized by elemental analysis, IR and 1H NMR. Solution reactions of Mn(ClO4)2 or MnCl2·4H2O with H4L in air generated a tetranuclear complex [MnIII4(HL)2(H2L)2(MeCN)4](ClO4)2·2MeCN (1) and a decanuclear complex [MnIII6MnII4(bz)10(L)4(H2O)2]·10MeCN (2), respectively. X-ray studies reveal that complex 1 crystallizes in triclinic space group P1, while complex 2 crystallizes in orthorhombic space group Aba2. Magnetism data in the temperature range 2~300 K have been carried out, indicating the presence of the antiferromagnetic interaction within 2.
A multidentate salicylaldehyde Schiff-base ligand with {NO4} donor set, 3, 5-di-tert-butylsalicylaldehyde-trihydroxymethylaminomethane (H4L), has been synthesized for the first time and characterized by elemental analysis, IR and 1H NMR. Solution reactions of Mn(ClO4)2 or MnCl2·4H2O with H4L in air generated a tetranuclear complex [MnIII4(HL)2(H2L)2(MeCN)4](ClO4)2·2MeCN (1) and a decanuclear complex [MnIII6MnII4(bz)10(L)4(H2O)2]·10MeCN (2), respectively. X-ray studies reveal that complex 1 crystallizes in triclinic space group P1, while complex 2 crystallizes in orthorhombic space group Aba2. Magnetism data in the temperature range 2~300 K have been carried out, indicating the presence of the antiferromagnetic interaction within 2.
2015, 31(9): 1839-1846
doi: 10.11862/CJIC.2015.242
Abstract:
A novel alkoxysilane (Cz-Si) was synthesized and used as an active reagent for self-assembled monolayer (SAM) modification on indium tin oxide (ITO) surface. The as-prepared Cz-Si could modify the ITO surface successfully under the mild atmosphere without any protection, offering simple and easy experimental operation. To investigate the effect of SAM modification on the device performances, based on ITO/SAM anodes, a series of organic light-emitting diodes (OLEDs) were fabricated: ITO/SAM (or unmodified)/NPB (40~50 nm)/Alq3 (60 nm)/LiF (1.0 nm)/Al. The devices show improvement compared to their counterparts with bare ITO anodes. The improvement could be attributed to the modulating of the electronic energy, surface roughness and interface integrity at the ITO/hole transporting layer (HTL) interface by SAM modification.
A novel alkoxysilane (Cz-Si) was synthesized and used as an active reagent for self-assembled monolayer (SAM) modification on indium tin oxide (ITO) surface. The as-prepared Cz-Si could modify the ITO surface successfully under the mild atmosphere without any protection, offering simple and easy experimental operation. To investigate the effect of SAM modification on the device performances, based on ITO/SAM anodes, a series of organic light-emitting diodes (OLEDs) were fabricated: ITO/SAM (or unmodified)/NPB (40~50 nm)/Alq3 (60 nm)/LiF (1.0 nm)/Al. The devices show improvement compared to their counterparts with bare ITO anodes. The improvement could be attributed to the modulating of the electronic energy, surface roughness and interface integrity at the ITO/hole transporting layer (HTL) interface by SAM modification.
2015, 31(9): 1847-1854
doi: 10.11862/CJIC.2015.236
Abstract:
Two dysprosium complexes, [Dy2(OAc)6H2O]n (1) and {[DyL(H2O)4]ClO4·H2O}n (2) (L=2, 2'-dithiobis(3-pyridinecarboxylic acid)), were synthesized and structurally and magnetically characterized. Complex 1 is a 1D dysprosium chain, in which the dysprosium ions are bridged by OAc- anions, exhibiting slow magnetic relaxation behavior with an energy barrier of 2 K. Complex 2 is a 2D dysprosium network, in which the carboxylato-bridged dysprosium chains are linked by disulfide bonds, showing ferromagnetic interaction and slow magnetic relaxation.
Two dysprosium complexes, [Dy2(OAc)6H2O]n (1) and {[DyL(H2O)4]ClO4·H2O}n (2) (L=2, 2'-dithiobis(3-pyridinecarboxylic acid)), were synthesized and structurally and magnetically characterized. Complex 1 is a 1D dysprosium chain, in which the dysprosium ions are bridged by OAc- anions, exhibiting slow magnetic relaxation behavior with an energy barrier of 2 K. Complex 2 is a 2D dysprosium network, in which the carboxylato-bridged dysprosium chains are linked by disulfide bonds, showing ferromagnetic interaction and slow magnetic relaxation.
2015, 31(9): 1855-1859
doi: 10.11862/CJIC.2015.256
Abstract:
A porous aromatic framework, PAF-9 derived from tetraphenylgermane as basic building unit, was synthesized via Friedel-Crafts alkylation reaction. The microstructure and pore property were investigated by FTIR spectroscopy, powder X-ray diffraction, solid state NMR, thermogravimetric analysis and low temperature N2 adsorption-desorption measurements. The characterizations reveal that PAF-9 possess high thermal and chemical stability as well as high BET surface area of 334 m2·g-1. Additionally, the resulting PAF materials exhibit high CO2 adsorption ability.
A porous aromatic framework, PAF-9 derived from tetraphenylgermane as basic building unit, was synthesized via Friedel-Crafts alkylation reaction. The microstructure and pore property were investigated by FTIR spectroscopy, powder X-ray diffraction, solid state NMR, thermogravimetric analysis and low temperature N2 adsorption-desorption measurements. The characterizations reveal that PAF-9 possess high thermal and chemical stability as well as high BET surface area of 334 m2·g-1. Additionally, the resulting PAF materials exhibit high CO2 adsorption ability.
2015, 31(9): 1860-1866
doi: 10.11862/CJIC.2015.248
Abstract:
Based on the survey of Gd-Cu complexes in literatures, a family of {LnCu3} clusters (Ln=Gd (1), Tb (2), Dy (3)) were selected to study the magnetocaloric effect (MCE) at low temperature due to their isolated Gd-Cu arrangement as well as the pure intramolecular ferromagnetic coupling. A modified one-pot synthetic method based on the reported result was developed to simplify the reaction procedure. Elementary analyses, IR, single crystal/powder X-ray diffraction measurements were carried out to determine the isomorphism and phase purity. Studies of MCEs indicate that complexes 1~3 have a maximum magnetic entropy change (-ΔSm) of 16.1 (2 K), 6.9 (5 K) and 8.1 (5 K) J·kg-1·k-1 for ΔH=0~7 T, respectively. Comparison of the MCE for {GdCu3} with the reported Gd-Cu clusters emphasizes the importance of weak ferromagnetic interactions in designing of 3d-4f molecular coolers.
Based on the survey of Gd-Cu complexes in literatures, a family of {LnCu3} clusters (Ln=Gd (1), Tb (2), Dy (3)) were selected to study the magnetocaloric effect (MCE) at low temperature due to their isolated Gd-Cu arrangement as well as the pure intramolecular ferromagnetic coupling. A modified one-pot synthetic method based on the reported result was developed to simplify the reaction procedure. Elementary analyses, IR, single crystal/powder X-ray diffraction measurements were carried out to determine the isomorphism and phase purity. Studies of MCEs indicate that complexes 1~3 have a maximum magnetic entropy change (-ΔSm) of 16.1 (2 K), 6.9 (5 K) and 8.1 (5 K) J·kg-1·k-1 for ΔH=0~7 T, respectively. Comparison of the MCE for {GdCu3} with the reported Gd-Cu clusters emphasizes the importance of weak ferromagnetic interactions in designing of 3d-4f molecular coolers.
2015, 31(9): 1867-1874
doi: 10.11862/CJIC.2015.226
Abstract:
Two TMeQ[6]-supported sandwich tetranuclear complexes, [Ln4(μ3-OH)4(μ2-OH)2(H2O)4(NO3)2 (TMeQ[6])2](NO3)4·26H2O (Ln=Dy, 1; Ln=Tb, 2), have been prepared and characterized. Crystal structural analysis reveals that both complexes contain a cubane-like [Ln4(μ3-OH)4]8+ cluster core sandwiched between two TMeQ[6] macro-cycles. Magnetic investigations indicate that complex 1 displays slow magnetization relaxation. Complex 2 exhibits intense photoluminescence owing to the efficient energy transfer from TMeQ[6] ligand to Tb3+ ion.
Two TMeQ[6]-supported sandwich tetranuclear complexes, [Ln4(μ3-OH)4(μ2-OH)2(H2O)4(NO3)2 (TMeQ[6])2](NO3)4·26H2O (Ln=Dy, 1; Ln=Tb, 2), have been prepared and characterized. Crystal structural analysis reveals that both complexes contain a cubane-like [Ln4(μ3-OH)4]8+ cluster core sandwiched between two TMeQ[6] macro-cycles. Magnetic investigations indicate that complex 1 displays slow magnetization relaxation. Complex 2 exhibits intense photoluminescence owing to the efficient energy transfer from TMeQ[6] ligand to Tb3+ ion.
2015, 31(9): 1875-1880
doi: 10.11862/CJIC.2015.238
Abstract:
KBi4F13 was synthesized by hydrothermal reaction of KF and Bi2O3 in aqueous solution of HF. Its crystal structure was determined by X-ray diffraction on the single crystal for the first time. Its potential as a new mid-IR nonlinear optical (NLO) material has been investigated. Its powders exhibit a phase-matchable second harmonic generation (SHG) effect as strong as a half of KDP. The laser damage threshold (LDT) value of its powders is measured to be 120 MW·cm-2, which is much higher than that of the currently commercialized IR NLO material AgGaS2 (5 MW·cm-2, measured in the same condition). Its powders show the transparent window in infrared region up to 20 μm, and it is thermally stable up to 220℃. These results indicate that KBi4F13 is a potentially useful new mid-IR NLO material with a high LDT.
KBi4F13 was synthesized by hydrothermal reaction of KF and Bi2O3 in aqueous solution of HF. Its crystal structure was determined by X-ray diffraction on the single crystal for the first time. Its potential as a new mid-IR nonlinear optical (NLO) material has been investigated. Its powders exhibit a phase-matchable second harmonic generation (SHG) effect as strong as a half of KDP. The laser damage threshold (LDT) value of its powders is measured to be 120 MW·cm-2, which is much higher than that of the currently commercialized IR NLO material AgGaS2 (5 MW·cm-2, measured in the same condition). Its powders show the transparent window in infrared region up to 20 μm, and it is thermally stable up to 220℃. These results indicate that KBi4F13 is a potentially useful new mid-IR NLO material with a high LDT.
2015, 31(9): 1881-1884
doi: 10.11862/CJIC.2015.259
Abstract:
The 1D coordination polymer [Zn(CH3COO)2(4, 4'-bipy)]n (4, 4'-bipy=4, 4'-bipyridine) has been synthesized under a new way. Previous studies have revealed its crystal structure and luminescent properties. In this article, we demonstrate its electron-transfer photochromic behavior, which is conformed to our previously proposed design strategy for electron-transfer photochromic materials.
The 1D coordination polymer [Zn(CH3COO)2(4, 4'-bipy)]n (4, 4'-bipy=4, 4'-bipyridine) has been synthesized under a new way. Previous studies have revealed its crystal structure and luminescent properties. In this article, we demonstrate its electron-transfer photochromic behavior, which is conformed to our previously proposed design strategy for electron-transfer photochromic materials.
2015, 31(9): 1885-1893
doi: 10.11862/CJIC.2015.251
Abstract:
Upon heating the initial mixture with the composition of nAl2O3:nP2O5:nen:nH2O=1:1:2:226 at 200℃ for 12 h, where en is ethylenediamine, a three-dimensional open-framework aluminophosphate AlPO4-12 was obtained. The crystallization process of AlPO4-12 was investigated using X-ray diffraction, elemental analysis, pH measurement, liquid NMR, and electrospray ionization mass spectra (ESI-MS). On the basis of the ESI-MS data, a method was developed to systematically enumerate the formula of the fragments formed during the crystallization of AlPO4-12. It was found that intermediate phases of layered aluminophosphates UiO-15 and UiO-13 were formed prior the crystallization of AlPO4-12. The concentration of Al species in the liquid throughout the crystallization was extremely low. A gradual increase of P-OH group in the P species in the liquid and a gradual protonation of ethylenediamine during the crystallization were observed. The formation of 4- and 6-membered rings was confirmed by the ESI-MS data. The utilization of ESI-MS in the investigation of the crystallization process of microporous crystalline materials may allow us to determine the structural information and the formula of the fragments formed during the crystallization.
Upon heating the initial mixture with the composition of nAl2O3:nP2O5:nen:nH2O=1:1:2:226 at 200℃ for 12 h, where en is ethylenediamine, a three-dimensional open-framework aluminophosphate AlPO4-12 was obtained. The crystallization process of AlPO4-12 was investigated using X-ray diffraction, elemental analysis, pH measurement, liquid NMR, and electrospray ionization mass spectra (ESI-MS). On the basis of the ESI-MS data, a method was developed to systematically enumerate the formula of the fragments formed during the crystallization of AlPO4-12. It was found that intermediate phases of layered aluminophosphates UiO-15 and UiO-13 were formed prior the crystallization of AlPO4-12. The concentration of Al species in the liquid throughout the crystallization was extremely low. A gradual increase of P-OH group in the P species in the liquid and a gradual protonation of ethylenediamine during the crystallization were observed. The formation of 4- and 6-membered rings was confirmed by the ESI-MS data. The utilization of ESI-MS in the investigation of the crystallization process of microporous crystalline materials may allow us to determine the structural information and the formula of the fragments formed during the crystallization.
2015, 31(9): 1894-1902
doi: 10.11862/CJIC.2015.240
Abstract:
By using carboxylate and chelating ligands, a family of tetranuclear lanthanide clusters, namely [Ln4(mnba)12(tzp)2(H2O)2] (Ln=Gd (1), Tb (2) and Er (3), Hmnba=m-nitrobenzoic acid, tzp=2-(1H-1, 2, 4-triazol-3-yl)pyridine), has been obtained under hydrothermal conditions. The three complexes exhibit linear tetranuclear clusters bridged by carboxylates with syn, syn-μ2-η1:η1 mode. Magnetic investigation indicates weak ferromagnetic interaction between adjacent GdⅢ or ErⅢ ions of the Ln4 cluster in 1 and 3, while weak intra-molecular antiferromagnetic interaction between TbⅢ ions and/or depopulation of the TbⅢ excited Stark sub-levels in 2. Complex 1 exhibits a significant magnetocaloric effect with -ΔSmmax=20.6 J·kg-1·k-1 and ac susceptibility measurements reveal frequency- and temperature-dependent out-of-phase signal under 5 kOe dc field in 3, being typical slow magnetic relaxation behavior due to strong anisotropy of ErⅢ and ferromagnetic coupling.
By using carboxylate and chelating ligands, a family of tetranuclear lanthanide clusters, namely [Ln4(mnba)12(tzp)2(H2O)2] (Ln=Gd (1), Tb (2) and Er (3), Hmnba=m-nitrobenzoic acid, tzp=2-(1H-1, 2, 4-triazol-3-yl)pyridine), has been obtained under hydrothermal conditions. The three complexes exhibit linear tetranuclear clusters bridged by carboxylates with syn, syn-μ2-η1:η1 mode. Magnetic investigation indicates weak ferromagnetic interaction between adjacent GdⅢ or ErⅢ ions of the Ln4 cluster in 1 and 3, while weak intra-molecular antiferromagnetic interaction between TbⅢ ions and/or depopulation of the TbⅢ excited Stark sub-levels in 2. Complex 1 exhibits a significant magnetocaloric effect with -ΔSmmax=20.6 J·kg-1·k-1 and ac susceptibility measurements reveal frequency- and temperature-dependent out-of-phase signal under 5 kOe dc field in 3, being typical slow magnetic relaxation behavior due to strong anisotropy of ErⅢ and ferromagnetic coupling.
2015, 31(9): 1903-1912
doi: 10.11862/CJIC.2015.253
Abstract:
Chemical functional groups of -CH3, -COOH and -OH have been introduced to the surface of AuNPs, separately. The AuNPs, Au-OH NPs, Au-COOH NPs and Au-CH3 NPs are spherical with dimension of (15.6±3.2) nm, displaying negative ζ potentials. The cytotoxicity of these AuNPs has been evaluated by methylthiazoletetrazolium (MTT) assay against Hela cells and MCG-803 cells in vitro, separately. MTT data reveal that the surface unmodified AuNPs exhibit low cytotoxicity at the highest concentration of 197 ng·mL-1 for both HeLa and MCG-803 cells in vitro. The surface modified AuNPs can further decrease the inherently cytotoxicity that follows the order AuNPs > Au-CH3 NPs > Au-COOH NPs≈Au-OH NPs. Cell cycle analysis indicates that AuNPs cause cell cycle slightly arrest at the G2/M phase. Micro-Raman spectra of individual living HeLa cells demonstrate that the backbone and nucleic bases of DNA as well as the polar headgroup of phospholipid in cells are the probable target binding sites of AuNPs and Au-CH3 NPs. Whereas, the interfacial interactions are significantly reduced when cells are treated with Au-COOH NPs and Au-OH NPs. Our results on the interaction mechanisms between AuNPs and cells demonstrate that AuNPs modified with surface functional groups of -COOH or -OH can improve their cytocompatibility.
Chemical functional groups of -CH3, -COOH and -OH have been introduced to the surface of AuNPs, separately. The AuNPs, Au-OH NPs, Au-COOH NPs and Au-CH3 NPs are spherical with dimension of (15.6±3.2) nm, displaying negative ζ potentials. The cytotoxicity of these AuNPs has been evaluated by methylthiazoletetrazolium (MTT) assay against Hela cells and MCG-803 cells in vitro, separately. MTT data reveal that the surface unmodified AuNPs exhibit low cytotoxicity at the highest concentration of 197 ng·mL-1 for both HeLa and MCG-803 cells in vitro. The surface modified AuNPs can further decrease the inherently cytotoxicity that follows the order AuNPs > Au-CH3 NPs > Au-COOH NPs≈Au-OH NPs. Cell cycle analysis indicates that AuNPs cause cell cycle slightly arrest at the G2/M phase. Micro-Raman spectra of individual living HeLa cells demonstrate that the backbone and nucleic bases of DNA as well as the polar headgroup of phospholipid in cells are the probable target binding sites of AuNPs and Au-CH3 NPs. Whereas, the interfacial interactions are significantly reduced when cells are treated with Au-COOH NPs and Au-OH NPs. Our results on the interaction mechanisms between AuNPs and cells demonstrate that AuNPs modified with surface functional groups of -COOH or -OH can improve their cytocompatibility.
2015, 31(9): 1913-1918
doi: 10.11862/CJIC.2015.239
Abstract:
A new kind of highly fluorescent AuNCs functionalized with β-cyclodextrin (CD) was prepared by using one-pot aqueous reduction of gold precursor. Aqueous dispersion of these red AuNCs exhibits good long-term colloidal stability as well as fluorescent stability. The average diameter of AuNCs-CD is (1.40±0.32) nm as determined by transmission electron microscopy (TEM). Confocal microscopic observation shows that AuNCs-CD can penetrate into cells and mainly localize within the cytoplasm. In vitro cytotoxicity assay indicates that the AuNCs-CD displays very low cytotoxicity against human lung adenocarcinoma A549 cells. Cyclodextrin modification is expected to make AuNCs more versatile for encapsulation of hydrophobic drugs and functionalization with targeting moieties, which will broaden the potential of AuNCs-CD for biomedical applications.
A new kind of highly fluorescent AuNCs functionalized with β-cyclodextrin (CD) was prepared by using one-pot aqueous reduction of gold precursor. Aqueous dispersion of these red AuNCs exhibits good long-term colloidal stability as well as fluorescent stability. The average diameter of AuNCs-CD is (1.40±0.32) nm as determined by transmission electron microscopy (TEM). Confocal microscopic observation shows that AuNCs-CD can penetrate into cells and mainly localize within the cytoplasm. In vitro cytotoxicity assay indicates that the AuNCs-CD displays very low cytotoxicity against human lung adenocarcinoma A549 cells. Cyclodextrin modification is expected to make AuNCs more versatile for encapsulation of hydrophobic drugs and functionalization with targeting moieties, which will broaden the potential of AuNCs-CD for biomedical applications.
2015, 31(9): 1667-1677
doi: 10.11862/CJIC.2015.241
Abstract:
The anti-tumor study of metal complexes, especially the platinum-base drugs, has achieved remarkable success but still facing several problems such as drugs resistance and side effects. Recently, ruthenium complexes attract many scientists' interests with their brand new application of anti-tumor drugs. In the series of non-platinum drugs, ruthenium complexes are regarded as one of the most potential anti-tumor drugs for the reason not merely the metal ruthenium and its complexes exhibit low toxicity but also they can be efficiently absorbed and excreted for human body. Herein, the study of the follow-up inhibition towards nucleus enzymes induced by the binding between ruthenium complexes and DNA was expatiated, introducing the advance anti-tumor applications of ruthenium complexes in new perspectives.
The anti-tumor study of metal complexes, especially the platinum-base drugs, has achieved remarkable success but still facing several problems such as drugs resistance and side effects. Recently, ruthenium complexes attract many scientists' interests with their brand new application of anti-tumor drugs. In the series of non-platinum drugs, ruthenium complexes are regarded as one of the most potential anti-tumor drugs for the reason not merely the metal ruthenium and its complexes exhibit low toxicity but also they can be efficiently absorbed and excreted for human body. Herein, the study of the follow-up inhibition towards nucleus enzymes induced by the binding between ruthenium complexes and DNA was expatiated, introducing the advance anti-tumor applications of ruthenium complexes in new perspectives.
2015, 31(9): 1678-1686
doi: 10.11862/CJIC.2015.257
Abstract:
Perovskite solar cells have been receiving intensive attentions and become a hot research topic in solar cells, due to their high photo-to-electric conversion efficiency, low manufacturing cost and simple fabrication process. In perovskite solar cell, the inorganic-organic hybrid ABX3 material functions as light absorbing layer as well as charge carrier transporting material. Therefore, the properties of ABX3 will directly affect the performance of perovskite solar cell. In this paper, we review on the present methods to tune the structure and properties of inorganic-organic hybrid ABX3 type perovskite photovoltaic material.
Perovskite solar cells have been receiving intensive attentions and become a hot research topic in solar cells, due to their high photo-to-electric conversion efficiency, low manufacturing cost and simple fabrication process. In perovskite solar cell, the inorganic-organic hybrid ABX3 material functions as light absorbing layer as well as charge carrier transporting material. Therefore, the properties of ABX3 will directly affect the performance of perovskite solar cell. In this paper, we review on the present methods to tune the structure and properties of inorganic-organic hybrid ABX3 type perovskite photovoltaic material.
2015, 31(9): 1687-1704
doi: 10.11862/CJIC.2015.252
Abstract:
The important roles of anions in biology, medicine, catalysis and environmental science have been widely recognized. Anion receptors showed bright application prospects in the trans epithelial ion transportation, chemical sensing, simulation of enzyme catalyzed organic reactions. Here we summarize the recent progress of anion receptors based on different hydrogen bonding units such as amide, urea/thiourea, indole/pyrroles, triazole, ammonium, guanidinium, imidazole, hydroxyl groups.
The important roles of anions in biology, medicine, catalysis and environmental science have been widely recognized. Anion receptors showed bright application prospects in the trans epithelial ion transportation, chemical sensing, simulation of enzyme catalyzed organic reactions. Here we summarize the recent progress of anion receptors based on different hydrogen bonding units such as amide, urea/thiourea, indole/pyrroles, triazole, ammonium, guanidinium, imidazole, hydroxyl groups.
2015, 31(9): 1705-1725
doi: 10.11862/CJIC.2015.247
Abstract:
Due to the advantages of their regulated composition, structure and size, redox activity and low corrosivity, etc., polyoxovanadium clusters have broad application prospects in the field of optical, magnetic, catalytic, medicine and become one of the hot research topics of polyoxometalates chemistry. Based on the recent investigations, this paper summarizes the related advancements in the synthesis, structure and properties of polyoxovanadium clusters and gives their researching prospects.
Due to the advantages of their regulated composition, structure and size, redox activity and low corrosivity, etc., polyoxovanadium clusters have broad application prospects in the field of optical, magnetic, catalytic, medicine and become one of the hot research topics of polyoxometalates chemistry. Based on the recent investigations, this paper summarizes the related advancements in the synthesis, structure and properties of polyoxovanadium clusters and gives their researching prospects.
2015, 31(9): 1726-1738
doi: 10.11862/CJIC.2015.254
Abstract:
Crystal defects are fundamental issues that define the physical and chemical properties in inorganic solid state chemistry. Memristive effects, which are mainly controlled by defects migration in solid state, will bring new revolution to the future electronic information industry. In this review, recent progress of memrisive effect in inorganic solid state materials was summarized. Main mechanism and material types are discussed in detail. These phenomena are highly related to atomic-scale p-n junction in manganite. This review indicates that defect transport mechanism study in electric field is an very important aspects in memristive applications.
Crystal defects are fundamental issues that define the physical and chemical properties in inorganic solid state chemistry. Memristive effects, which are mainly controlled by defects migration in solid state, will bring new revolution to the future electronic information industry. In this review, recent progress of memrisive effect in inorganic solid state materials was summarized. Main mechanism and material types are discussed in detail. These phenomena are highly related to atomic-scale p-n junction in manganite. This review indicates that defect transport mechanism study in electric field is an very important aspects in memristive applications.
2015, 31(9): 1739-1750
doi: 10.11862/CJIC.2015.258
Abstract:
Sodium ion batteries (SIBs) have recently attracted much attention because of the abundance, wide distribution and low cost of Na source. However, Na+ is heavier and larger than that of Li+, limiting the insertion of and extraction of Na+ into and from the host materials. Thus, developing the advanced electrodes materials is the key point for SIBs. In this review, we summarize the research development of selected electrode materials of SIBs. This should shed light on the R & D of advanced electrode materials of SIBs.
Sodium ion batteries (SIBs) have recently attracted much attention because of the abundance, wide distribution and low cost of Na source. However, Na+ is heavier and larger than that of Li+, limiting the insertion of and extraction of Na+ into and from the host materials. Thus, developing the advanced electrodes materials is the key point for SIBs. In this review, we summarize the research development of selected electrode materials of SIBs. This should shed light on the R & D of advanced electrode materials of SIBs.
2015, 31(9): 1751-1760
doi: 10.11862/CJIC.2015.255
Abstract:
Quantum-dots (QDs) usually show pure color and bright emission with a core-shell structure. In particular, Ⅱ-Ⅵ semiconductor QDs applied in light-emitting diodes (LEDs) are highlighted in this review for excellent performance and controllable synthesis. The structures of QD and LED, as well as charge transport materials, have to be designed and optimized for high external quantum efficiency (EQE). As QD-LED efficiencies approach those of Organic LED (OLED), the key challenges facing commercialization are addressed.
Quantum-dots (QDs) usually show pure color and bright emission with a core-shell structure. In particular, Ⅱ-Ⅵ semiconductor QDs applied in light-emitting diodes (LEDs) are highlighted in this review for excellent performance and controllable synthesis. The structures of QD and LED, as well as charge transport materials, have to be designed and optimized for high external quantum efficiency (EQE). As QD-LED efficiencies approach those of Organic LED (OLED), the key challenges facing commercialization are addressed.
