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2014 Volume 30 Issue 1
2014, 30(1): 1-9
doi: 10.11862/CJIC.2014.072
Abstract:
Calcium phosphate nanoparticles play a key role in the formation of bone in nature. Although there is significant variation between different types of bone, inorganic components in the primary structure of bone are nano calcium phosphates. Nano-calcium phosphates can confer on bone remarkable mechanical property and bioactivity. In living organisms, inorganic nano calcium phosphate particles, under the control of an organic matrix, can combine into self-assembled biominerals. The in vitro experiments have demonstrated the improved biocompatibility of calcium phosphates in their nano forms. Greater cell proliferation of bone marrow mesenchymal stem cells (MSCs) is frequently induced by smaller hydroxyapatite (HAP) nanoparticles. HAP improved a better differentiation for MSCs than the amorphous one, ACP, when they are in the same size distribution. Due to its excellent biocompatibility, it is suggest that nano-HAP may be developed as an ideal biomaterial in bone tissue engineering and biomedicine.
Calcium phosphate nanoparticles play a key role in the formation of bone in nature. Although there is significant variation between different types of bone, inorganic components in the primary structure of bone are nano calcium phosphates. Nano-calcium phosphates can confer on bone remarkable mechanical property and bioactivity. In living organisms, inorganic nano calcium phosphate particles, under the control of an organic matrix, can combine into self-assembled biominerals. The in vitro experiments have demonstrated the improved biocompatibility of calcium phosphates in their nano forms. Greater cell proliferation of bone marrow mesenchymal stem cells (MSCs) is frequently induced by smaller hydroxyapatite (HAP) nanoparticles. HAP improved a better differentiation for MSCs than the amorphous one, ACP, when they are in the same size distribution. Due to its excellent biocompatibility, it is suggest that nano-HAP may be developed as an ideal biomaterial in bone tissue engineering and biomedicine.
2014, 30(1): 10-19
doi: 10.11862/CJIC.2014.071
Abstract:
Over the past few years, thermoelectric materials have redrawn considerable attentions among physics, chemistry, and materials researchers due to their capability of direct conversion between heat and electricity, which is today well recognized as viable renewable-energy sources. However, it is still one of the biggest challenges hitherto to independently optimize these three parameters for obtaining high-performance thermoelectric materials with large ZT value. Chalcogenide semiconductors as the most important class of thermoelectric materials, the synergistic optimization of their electrical-thermal transport properties has attracted widespread attentions. Herein, we reviewed the latest development of the synergistic optimization in Chalcogenide semiconductors. We also analyzed the inherent physical mechanisms within the synergistic optimization. Finally, we summarized the prospects of these new strategies in thermoelectric materials development.
Over the past few years, thermoelectric materials have redrawn considerable attentions among physics, chemistry, and materials researchers due to their capability of direct conversion between heat and electricity, which is today well recognized as viable renewable-energy sources. However, it is still one of the biggest challenges hitherto to independently optimize these three parameters for obtaining high-performance thermoelectric materials with large ZT value. Chalcogenide semiconductors as the most important class of thermoelectric materials, the synergistic optimization of their electrical-thermal transport properties has attracted widespread attentions. Herein, we reviewed the latest development of the synergistic optimization in Chalcogenide semiconductors. We also analyzed the inherent physical mechanisms within the synergistic optimization. Finally, we summarized the prospects of these new strategies in thermoelectric materials development.
2014, 30(1): 20-36
doi: 10.11862/CJIC.2014.068
Abstract:
The N-heterocyclic carbene (NHC) chemistry of copper has been flourishing in the past two decades. Cu-NHC complexes are of low cost and low toxicity which are easily available via various synthetic routes. Their structural diversity and ease of structural modification offer excellent opportunities for their versatile applications in the fields of catalysis, medicine, and materials. This review summarizes the synthetic routes to Cu-NHC complexes, structural features, carbene transfer reactivities and their applications in synthesis of other metal-NHC complexes, as well as their applications in catalysis.
The N-heterocyclic carbene (NHC) chemistry of copper has been flourishing in the past two decades. Cu-NHC complexes are of low cost and low toxicity which are easily available via various synthetic routes. Their structural diversity and ease of structural modification offer excellent opportunities for their versatile applications in the fields of catalysis, medicine, and materials. This review summarizes the synthetic routes to Cu-NHC complexes, structural features, carbene transfer reactivities and their applications in synthesis of other metal-NHC complexes, as well as their applications in catalysis.
2014, 30(1): 37-52
doi: 10.11862/CJIC.2014.084
Abstract:
Recent advances on the experimental and computational studies of interactions between humic acids (HAs) and actinides are briefly reviewed. It appears that HAs are able to form coordination complexes with actinide cations (Ann+) mainly via their carboxylate groups, and as a consequence, influence the migration of Ann+. In geomedia, many factors may affect the interactions between HA and Ann+, including pH, ionic strength, mineral surfaces, among which the effect of pH is the most significant. In general, at low pH, HA may enhance the adsorption of Ann+ on the surface of minerals, while when pH is around or larger than7, HA plays an opposite role. In addition, HAs may reduce high valent oxidative actinide cations, and the reductivity originates from their quinoid and phenol groups. In those HAs with high presence of reduced sulfur, HAs may become more redox sensitive due to the participation of Sin the redox reactions. The paper is concluded with an outlook.
Recent advances on the experimental and computational studies of interactions between humic acids (HAs) and actinides are briefly reviewed. It appears that HAs are able to form coordination complexes with actinide cations (Ann+) mainly via their carboxylate groups, and as a consequence, influence the migration of Ann+. In geomedia, many factors may affect the interactions between HA and Ann+, including pH, ionic strength, mineral surfaces, among which the effect of pH is the most significant. In general, at low pH, HA may enhance the adsorption of Ann+ on the surface of minerals, while when pH is around or larger than7, HA plays an opposite role. In addition, HAs may reduce high valent oxidative actinide cations, and the reductivity originates from their quinoid and phenol groups. In those HAs with high presence of reduced sulfur, HAs may become more redox sensitive due to the participation of Sin the redox reactions. The paper is concluded with an outlook.
2014, 30(1): 53-61
doi: 10.11862/CJIC.2014.083
Abstract:
Hydroaminoalkylation of alkenes has attracted intense interest over the past few years for its high atom efficiency. In the reactions, the α C-H bonds of N-alkylamines are added to alkenes to afford new amines in a single step with no by-product. This review provides an overview of recent developments in the transition metal-catalyzed intra-and inter-molecular hydroaminoalkylation of alkenes. Mechanistic studies of the reactions are also discussed.
Hydroaminoalkylation of alkenes has attracted intense interest over the past few years for its high atom efficiency. In the reactions, the α C-H bonds of N-alkylamines are added to alkenes to afford new amines in a single step with no by-product. This review provides an overview of recent developments in the transition metal-catalyzed intra-and inter-molecular hydroaminoalkylation of alkenes. Mechanistic studies of the reactions are also discussed.
2014, 30(1): 62-74
doi: 10.11862/CJIC.2014.070
Abstract:
Field emission has been widely used in many areas, such as scanning electron microscopy, plane display device, pressure sensor, acceleration sensor and electron beam addressed memory devices etc. Molecular materials are potential candidates for future field emission cathode materials, due to their notable characteristics of adjustable structures and energy bands, flexible nature, and easy processing. In this work, we will review some field emission properties of aggregation structure based molecular materials, especially, the effects of size and morphology based on field emission properties of molecular materials are described in detailed. The aim of review provides an intuition for understanding the structure-function relationships in molecular materials, which could lead to new design concepts for the development of new high field emission performance molecular materials on aggregate nanostructures.
Field emission has been widely used in many areas, such as scanning electron microscopy, plane display device, pressure sensor, acceleration sensor and electron beam addressed memory devices etc. Molecular materials are potential candidates for future field emission cathode materials, due to their notable characteristics of adjustable structures and energy bands, flexible nature, and easy processing. In this work, we will review some field emission properties of aggregation structure based molecular materials, especially, the effects of size and morphology based on field emission properties of molecular materials are described in detailed. The aim of review provides an intuition for understanding the structure-function relationships in molecular materials, which could lead to new design concepts for the development of new high field emission performance molecular materials on aggregate nanostructures.
2014, 30(1): 75-84
doi: 10.11862/CJIC.2014.034
Abstract:
Iridium(Ⅲ) porphyrin β-hydroxyethyl, IrⅢ(ttp)CH2CH2OH (ttp=5,10,15,20-tetratolylporphyrinato dianion), was found to selectively cleave the aldehydic carbon-hydrogen bonds of aryl aldehydes giving iridium acyl complexes. Iridium acyl complexes are good candidates for the studies on carbonylation and decarbonylation reactions as well as potential functionalization. The carbon-hydrogen bond activation (CHA) is proposed to occur through the initial β-hydroxyl elimination of IrⅢ(ttp)CH2CH2OH to give IrⅢ(ttp)OH, which then undergoes σ-bond metathesis with the aldehydic C-H bond.
Iridium(Ⅲ) porphyrin β-hydroxyethyl, IrⅢ(ttp)CH2CH2OH (ttp=5,10,15,20-tetratolylporphyrinato dianion), was found to selectively cleave the aldehydic carbon-hydrogen bonds of aryl aldehydes giving iridium acyl complexes. Iridium acyl complexes are good candidates for the studies on carbonylation and decarbonylation reactions as well as potential functionalization. The carbon-hydrogen bond activation (CHA) is proposed to occur through the initial β-hydroxyl elimination of IrⅢ(ttp)CH2CH2OH to give IrⅢ(ttp)OH, which then undergoes σ-bond metathesis with the aldehydic C-H bond.
2014, 30(1): 85-92
doi: 10.11862/CJIC.2014.074
Abstract:
Two compounds with L-Chiral helical chains have been solvothermal synthesized: Sm(HCO2)(SO4)(H2O) (1) and KSm(H2O)(SO4)2 (2). Complex 1 is synthesized without any chiral auxiliary, while complex 2 is the opposite. However, in 2, chiral auxiliaries do not exsit in the inorganic framework but work as the inducer in the formation of the complex. Single-crystal X-ray diffraction (XRD) demonstrates that complex 1 crystallizes in space group P41 and complex 2 crystallizes in space group P31. Complex 1 is constructed of two types of L-[Sm-O]n chains, every two different kinds of adjacent helical chains are connected by sharing Sm(Ⅲ) ions to form Intertwined left-handed double helices. Compound 2 is constructed of two L-chiral helical chains: [Sm-O-S1-O]n and [Sm-O-S2-O]n, the two adjacent helical chains are connected by sharing Sm(Ⅲ) ions to form double helices chains, every two adjacent double helices chains are connected through K+ linkages to form Intertwined left-handed double helices. The second-harmonic-generation efficiencies and fluorescence of 1 and 2 were studied.
Two compounds with L-Chiral helical chains have been solvothermal synthesized: Sm(HCO2)(SO4)(H2O) (1) and KSm(H2O)(SO4)2 (2). Complex 1 is synthesized without any chiral auxiliary, while complex 2 is the opposite. However, in 2, chiral auxiliaries do not exsit in the inorganic framework but work as the inducer in the formation of the complex. Single-crystal X-ray diffraction (XRD) demonstrates that complex 1 crystallizes in space group P41 and complex 2 crystallizes in space group P31. Complex 1 is constructed of two types of L-[Sm-O]n chains, every two different kinds of adjacent helical chains are connected by sharing Sm(Ⅲ) ions to form Intertwined left-handed double helices. Compound 2 is constructed of two L-chiral helical chains: [Sm-O-S1-O]n and [Sm-O-S2-O]n, the two adjacent helical chains are connected by sharing Sm(Ⅲ) ions to form double helices chains, every two adjacent double helices chains are connected through K+ linkages to form Intertwined left-handed double helices. The second-harmonic-generation efficiencies and fluorescence of 1 and 2 were studied.
2014, 30(1): 93-98
doi: 10.11862/CJIC.2014.080
Abstract:
Anew dinuclear Dy(Ⅲ) β-diketonate complex, Dy2(Hpdm)2(dbm)4·2EtOH (1, H2pdm=2,6-pyridinedimethanol, Hdbm=dibenzoylmethane), has been successfully prepared by ultrasonic method. Single crystal X-ray crystallographic analysis revealed that the two Dy(Ⅲ) ions are bridged by the deprotonated alkoxide arm of the pdmH-ligand. Variable-temperature magnetic susceptibility measurements showed that there exists a weak antiferromagnetic interaction between the two Dy(Ⅲ) ions, but no relaxation process of magnetion was observed, even when a 2000 Oe dc field was applied.
Anew dinuclear Dy(Ⅲ) β-diketonate complex, Dy2(Hpdm)2(dbm)4·2EtOH (1, H2pdm=2,6-pyridinedimethanol, Hdbm=dibenzoylmethane), has been successfully prepared by ultrasonic method. Single crystal X-ray crystallographic analysis revealed that the two Dy(Ⅲ) ions are bridged by the deprotonated alkoxide arm of the pdmH-ligand. Variable-temperature magnetic susceptibility measurements showed that there exists a weak antiferromagnetic interaction between the two Dy(Ⅲ) ions, but no relaxation process of magnetion was observed, even when a 2000 Oe dc field was applied.
2014, 30(1): 99-105
doi: 10.11862/CJIC.2014.081
Abstract:
Two new coordination polymers [Zn(L)(m-BDC)] (1) and [Cd(L)(CCA)]·2H2O (2) were synthesized by solvothermal method using 3,5-di(1H-benzoimidazol-1-yl)pyridine (L), isophthalic acid (m-H2BDC), 4-(2-carbox-yvinyl)benzoic acid (H2CCA). And the complexes were characterized by FT-IR, elemental analysis, thermogravimetric analysis (TGA) and power X-ray diffraction (PXRD), meanwhile the crystal structures and fluorescence properties of the complexes have been studied. In complex 1, the ligand Lconnects the metal atoms to give a 1Dchain structure, and the m-BDC2- coordinates with metal atom to form a M2(m-BDC)2 unit (M=metal). Moreover, the adjacent 1D chains are linked by the M2(m-BDC)2 to produce a 2D network structure. In complex 2, the ligand joins the metal atoms to generate a 1D chain like that in 1. However, the carboxylate ligand coordinates with metal atoms to form a 1D chain, and two kinds of the 1D chains crosslink each other to produce a 2D structure.
Two new coordination polymers [Zn(L)(m-BDC)] (1) and [Cd(L)(CCA)]·2H2O (2) were synthesized by solvothermal method using 3,5-di(1H-benzoimidazol-1-yl)pyridine (L), isophthalic acid (m-H2BDC), 4-(2-carbox-yvinyl)benzoic acid (H2CCA). And the complexes were characterized by FT-IR, elemental analysis, thermogravimetric analysis (TGA) and power X-ray diffraction (PXRD), meanwhile the crystal structures and fluorescence properties of the complexes have been studied. In complex 1, the ligand Lconnects the metal atoms to give a 1Dchain structure, and the m-BDC2- coordinates with metal atom to form a M2(m-BDC)2 unit (M=metal). Moreover, the adjacent 1D chains are linked by the M2(m-BDC)2 to produce a 2D network structure. In complex 2, the ligand joins the metal atoms to generate a 1D chain like that in 1. However, the carboxylate ligand coordinates with metal atoms to form a 1D chain, and two kinds of the 1D chains crosslink each other to produce a 2D structure.
2014, 30(1): 106-112
doi: 10.11862/CJIC.2014.069
Abstract:
PvdAis a siderophore, secreted by Pseudomonas aeruginosa in order to get access to iron. PvdA in50 mmol·L-1 Tris-HCl, pH8.0 was titrated with acidic solutions of Tb3+ and the binding of Tb3+ to PvdA was followed from changes both in the difference UV-Vis spectra at 380 nm and in fluorescence at 457 nm. The 1:1 stable complex of Tb-PvdA can be confirmed from spectral titration curves. Using EDTAas a competitor the conditional binding constant of the complex was measured to be (4.44±0.82)×1014 mol-1·L. The formed Tb-PvdA from the reaction between PvdA and Tb3+ saturated ovotansferrin can be followed by measuring the fluorescence emission of Tb3+ at 548 nm, demonstrating that the binding of PvdA for Tb3+ is stronger than that of apoovotransferrin. Furthermore, Tb-PvdA interaction with the PvdA-Fe outer membrane transporter, FpvA, of Pseudomonas aeruginosa could be followed by fluorescence resonance energy transfer between the tryptophans of FpvA (donor) and PvdA (acceptor).
PvdAis a siderophore, secreted by Pseudomonas aeruginosa in order to get access to iron. PvdA in50 mmol·L-1 Tris-HCl, pH8.0 was titrated with acidic solutions of Tb3+ and the binding of Tb3+ to PvdA was followed from changes both in the difference UV-Vis spectra at 380 nm and in fluorescence at 457 nm. The 1:1 stable complex of Tb-PvdA can be confirmed from spectral titration curves. Using EDTAas a competitor the conditional binding constant of the complex was measured to be (4.44±0.82)×1014 mol-1·L. The formed Tb-PvdA from the reaction between PvdA and Tb3+ saturated ovotansferrin can be followed by measuring the fluorescence emission of Tb3+ at 548 nm, demonstrating that the binding of PvdA for Tb3+ is stronger than that of apoovotransferrin. Furthermore, Tb-PvdA interaction with the PvdA-Fe outer membrane transporter, FpvA, of Pseudomonas aeruginosa could be followed by fluorescence resonance energy transfer between the tryptophans of FpvA (donor) and PvdA (acceptor).
2014, 30(1): 113-120
doi: 10.11862/CJIC.2014.040
Abstract:
By co-doping Alq3[tris(8-hydroxyquinoline) aluminum] and Eu(TTA)3phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) into CBP (4,4'-N，N' dicarbazole-biphenyl), a series of electroluminescent (EL) devices were fabricated and investigated. After optimizing the co-doping concentration of Alq3, significant suppression of ELefficiency roll-off and almost doubled maximum brightness were realized without deteriorating the color purity. The presence of Alq3 molecules in light-emitting layer (EML) not only facilitates the injection and transport of electrons but also retards the transport of holes. Alq3 molecules function as ladders of hole transfer from CBP to Eu(TTA)3phen molecules as supported by the EL spectroscopy results, thus facilitating the balance of holes and electrons on Eu(TTA)3phen molecules. Therefore, two possible reasons are suggested to be responsible for the suppression of EL efficiency roll-off: one is the broadening of recombination zone, the other is the improved balance of holes and electrons on Eu(TTA)3phen molecules.
By co-doping Alq3[tris(8-hydroxyquinoline) aluminum] and Eu(TTA)3phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) into CBP (4,4'-N，N' dicarbazole-biphenyl), a series of electroluminescent (EL) devices were fabricated and investigated. After optimizing the co-doping concentration of Alq3, significant suppression of ELefficiency roll-off and almost doubled maximum brightness were realized without deteriorating the color purity. The presence of Alq3 molecules in light-emitting layer (EML) not only facilitates the injection and transport of electrons but also retards the transport of holes. Alq3 molecules function as ladders of hole transfer from CBP to Eu(TTA)3phen molecules as supported by the EL spectroscopy results, thus facilitating the balance of holes and electrons on Eu(TTA)3phen molecules. Therefore, two possible reasons are suggested to be responsible for the suppression of EL efficiency roll-off: one is the broadening of recombination zone, the other is the improved balance of holes and electrons on Eu(TTA)3phen molecules.
2014, 30(1): 121-126
doi: 10.11862/CJIC.2014.037
Abstract:
High yield and para-selective products were obtained by the nitration of methyl salicylate (MeS) and copper(Ⅱ) nitrate(CuN). The results of electron absorption spectra (EAS),Cyclic Voltammetry(CV) and electrospray ionization mass spectra (ESIMS) reveal that the reaction favors a radical nitration mechanism. It is the coordination of MeS with CuNthat promotes the splitting of N-O bonds of nitrate group in CuN, and results in the formation of nitro radicals, oxygen radicals and complex radicals. The nitro radicals can react with MeS or the complexes of MeS to form nitration products. The nitrated complexes immediately turn to methyl nitrosalicylate by Cu(Ⅱ) ions being hydrolyzed to copper(Ⅱ) oxides.
High yield and para-selective products were obtained by the nitration of methyl salicylate (MeS) and copper(Ⅱ) nitrate(CuN). The results of electron absorption spectra (EAS),Cyclic Voltammetry(CV) and electrospray ionization mass spectra (ESIMS) reveal that the reaction favors a radical nitration mechanism. It is the coordination of MeS with CuNthat promotes the splitting of N-O bonds of nitrate group in CuN, and results in the formation of nitro radicals, oxygen radicals and complex radicals. The nitro radicals can react with MeS or the complexes of MeS to form nitration products. The nitrated complexes immediately turn to methyl nitrosalicylate by Cu(Ⅱ) ions being hydrolyzed to copper(Ⅱ) oxides.
2014, 30(1): 127-133
doi: 10.11862/CJIC.2014.079
Abstract:
Highly dispersed palladium nanoparticles (Pd NPs) supported on zeolitic imidazolate frameworks (ZIFs) ZIF-8 (Pd/ZIF-8) have been prepared in situ via mechanochemical method. The Pd/ZIF-8 frameworks were characterized by XRD, N2 adsorption, TEM, ICP-AES and XPS. The results show that bulk production of highly dispersed palladium nanoparticles can be achieved by mechanochemical method. Moreover, the obtained Pd/ZIF-8 exhibits high activity for Suzuki-Miyaura cross-coupling reaction and can be easily recovered and reused.
Highly dispersed palladium nanoparticles (Pd NPs) supported on zeolitic imidazolate frameworks (ZIFs) ZIF-8 (Pd/ZIF-8) have been prepared in situ via mechanochemical method. The Pd/ZIF-8 frameworks were characterized by XRD, N2 adsorption, TEM, ICP-AES and XPS. The results show that bulk production of highly dispersed palladium nanoparticles can be achieved by mechanochemical method. Moreover, the obtained Pd/ZIF-8 exhibits high activity for Suzuki-Miyaura cross-coupling reaction and can be easily recovered and reused.
2014, 30(1): 134-141
doi: 10.11862/CJIC.2014.073
Abstract:
By introducing tetraphenylimidodiphosphinate (Htpip) as the ancillary ligand, two iridium complexes Ir(tfmpiq)2tpip and Ir(dfpiq)2tpip (dfpiq=2-(2,4-difluorophenyl)quinoline, tfmpiq=2-(4-(trifluoromethyl)phenyl)quinoline) have been synthesized. For the emission spectra in CH2Cl2 solution, the maximum peaks locate at 622 and 600 nm for Ir(tfmpiq)2tpip and Ir(dfpiq)2tpip with the quantum efficiencies of 15% and 17%, respectively. The HOMO/LUMO levels are calculated as-4.80/-2.58 and-4.73/-2.57 eV, respectively. Under electric field from 1150 to 1300 (V·cm-1)1/2, the electron mobilities in 60 nm Ir(tfmpiq)2tpip and Ir(dfpiq)2tpip layers are 6.61~8.49×10-6 cm2·V-1·s-1 and 6.08~6.61×10-6 cm2·V-1·s-1, respectively. The devices with the structure of ITO/TAPC(60 nm)/Ir-complex (15wt%): CBP (50 nm)/TPBi(60 nm)/LiF(1 nm)/Al(100 nm) were fabricated. The device based on Ir(dfpiq)2tpip exhibited a luminance of 18195 cd·m-2 at a driving voltage of 12.0 Vwith a maximum current efficiency (ηc) of 4.71 cd·A-1 and a maximum power efficiency (ηp) of 1.82 lm·W-1, respectively. While the device based on Ir(tfmpiq)2tpip exhibited a luminance of 14676 cd·m-2 at a driving voltage of 12.0 V with a maximum ηc of 3.47 cd·A-1 and ηp of 1.51 lm·W-1, respectively.
By introducing tetraphenylimidodiphosphinate (Htpip) as the ancillary ligand, two iridium complexes Ir(tfmpiq)2tpip and Ir(dfpiq)2tpip (dfpiq=2-(2,4-difluorophenyl)quinoline, tfmpiq=2-(4-(trifluoromethyl)phenyl)quinoline) have been synthesized. For the emission spectra in CH2Cl2 solution, the maximum peaks locate at 622 and 600 nm for Ir(tfmpiq)2tpip and Ir(dfpiq)2tpip with the quantum efficiencies of 15% and 17%, respectively. The HOMO/LUMO levels are calculated as-4.80/-2.58 and-4.73/-2.57 eV, respectively. Under electric field from 1150 to 1300 (V·cm-1)1/2, the electron mobilities in 60 nm Ir(tfmpiq)2tpip and Ir(dfpiq)2tpip layers are 6.61~8.49×10-6 cm2·V-1·s-1 and 6.08~6.61×10-6 cm2·V-1·s-1, respectively. The devices with the structure of ITO/TAPC(60 nm)/Ir-complex (15wt%): CBP (50 nm)/TPBi(60 nm)/LiF(1 nm)/Al(100 nm) were fabricated. The device based on Ir(dfpiq)2tpip exhibited a luminance of 18195 cd·m-2 at a driving voltage of 12.0 Vwith a maximum current efficiency (ηc) of 4.71 cd·A-1 and a maximum power efficiency (ηp) of 1.82 lm·W-1, respectively. While the device based on Ir(tfmpiq)2tpip exhibited a luminance of 14676 cd·m-2 at a driving voltage of 12.0 V with a maximum ηc of 3.47 cd·A-1 and ηp of 1.51 lm·W-1, respectively.
2014, 30(1): 142-148
doi: 10.11862/CJIC.2014.087
Abstract:
Three isostructural coordination polymers, namely [Ni(8-qoac)Cl]n (1, 8-Hqoac=quinoline-8-oxy-acetic acid), [Fe(8-qoac)Cl]n (2), and [Mn(8-qoac)Cl]n (3) were synthesized under solvothermal reaction conditions. Single-crystal X-ray diffraction studies showed that 1~3 crystallize in the same space group Pbca, in which the octahedral metal ions are first bridged by two chloride ions to form a dinuclear building blocks, and then each dinuclear building block is connected to four adjacent neighbors via four carboxylate groups with the anti-anti coordination mode, giving a two-dimensional layered (4, 4) network considering the dinuclear building blocks as 4-connected nodes and the carboxylate groups as linkers. Magnetic measurements revealed spin-canting-like behaviors for compound 1, while 2 and 3 only exhibit simple antiferromagnetic properties, which can be explained by the different magnetic anisotropic behaviors of the transition metal ions.
Three isostructural coordination polymers, namely [Ni(8-qoac)Cl]n (1, 8-Hqoac=quinoline-8-oxy-acetic acid), [Fe(8-qoac)Cl]n (2), and [Mn(8-qoac)Cl]n (3) were synthesized under solvothermal reaction conditions. Single-crystal X-ray diffraction studies showed that 1~3 crystallize in the same space group Pbca, in which the octahedral metal ions are first bridged by two chloride ions to form a dinuclear building blocks, and then each dinuclear building block is connected to four adjacent neighbors via four carboxylate groups with the anti-anti coordination mode, giving a two-dimensional layered (4, 4) network considering the dinuclear building blocks as 4-connected nodes and the carboxylate groups as linkers. Magnetic measurements revealed spin-canting-like behaviors for compound 1, while 2 and 3 only exhibit simple antiferromagnetic properties, which can be explained by the different magnetic anisotropic behaviors of the transition metal ions.
2014, 30(1): 149-154
doi: 10.11862/CJIC.2014.085
Abstract:
Anew hexanuclear CoⅡ complex, namely [Co6(TDA)4(H2O)14]·5H2O (1) (H3TDA=1H-1,2,3-triazole-4,5-dicarboxylic acid), has been successfully synthesized and characterized by infrared spectra, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic space group P21212, with cell parameters: a=1.64730(2) nm, b=1.65330(2) nm, c=0.732690(10) nm and Flack parameter of 0.00(13). In title complex, six CoⅡ ions are connected by four TDA3- ligands to form a hexanuclear CoⅡunit, which can be extended to a 3D supramolecular architecture through the hydrogen-bonding interactions. Magnetic study reveals the dominant antiferromagnetic interaction exist between CoⅡ ions in 1.
Anew hexanuclear CoⅡ complex, namely [Co6(TDA)4(H2O)14]·5H2O (1) (H3TDA=1H-1,2,3-triazole-4,5-dicarboxylic acid), has been successfully synthesized and characterized by infrared spectra, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffraction. Complex 1 crystallizes in orthorhombic space group P21212, with cell parameters: a=1.64730(2) nm, b=1.65330(2) nm, c=0.732690(10) nm and Flack parameter of 0.00(13). In title complex, six CoⅡ ions are connected by four TDA3- ligands to form a hexanuclear CoⅡunit, which can be extended to a 3D supramolecular architecture through the hydrogen-bonding interactions. Magnetic study reveals the dominant antiferromagnetic interaction exist between CoⅡ ions in 1.
2014, 30(1): 155-162
doi: 10.11862/CJIC.2014.075
Abstract:
Bioinspired TiO2 fibers with periodic spindle knots were prepared, whose surface showed responsive wettability and adhesion. The responsive wettability of these fibers was intellectually controlled by micro/nano structures of fibers and environmental stimulation such as ultraviolet and ultrasonic. Based on controlled wettability of bioinspired TiO2 fibers, tiny water droplets could not only move directionally from joint to spindle knot but also be captured by fiber spindle knots. When the fibers are hydrophilic, tiny water droplets always move directionally whatever the surface of fibers is smooth or rough. When the fibers become hydrophobic, tiny water droplets on the fibers firstly move from both ends to center of spindle knots, and then are adhered by spindle knots with rough surface.
Bioinspired TiO2 fibers with periodic spindle knots were prepared, whose surface showed responsive wettability and adhesion. The responsive wettability of these fibers was intellectually controlled by micro/nano structures of fibers and environmental stimulation such as ultraviolet and ultrasonic. Based on controlled wettability of bioinspired TiO2 fibers, tiny water droplets could not only move directionally from joint to spindle knot but also be captured by fiber spindle knots. When the fibers are hydrophilic, tiny water droplets always move directionally whatever the surface of fibers is smooth or rough. When the fibers become hydrophobic, tiny water droplets on the fibers firstly move from both ends to center of spindle knots, and then are adhered by spindle knots with rough surface.
2014, 30(1): 163-168
doi: 10.11862/CJIC.2014.067
Abstract:
Anew dinuclear cobalt(Ⅲ) complex, [Co2L3]·8H2O (1), (H2L=N，N'-bis(2-picolinoyl)hydrazine), was synthesized by a hydrothermal method and characterized by UV, FT-IR, ESI-MS, TGA, EA and single crystal X-ray crystallography. The complex crystallizes in trigonal system with space group R3c, a=1.63640(11) nm, α=48.52°, V=2.2556(3) nm3, Z=2, and final R=0.062. Each Co(Ⅲ) has an octahedral [CoN6] core. Each L2- ligand binds simultaneously to two Co(Ⅲ) cations in a bis(N，N')-bridging coordination mode with a Co…Co distance of 0.3497(2) nm. The hydrogen bonding interactions between carbonyl group and pyridyl ring link the molecules of 1 into a 1D chain which was further connected by the lattice water to form a 3D supramolecular framework. The TG analysis shows that 1 loses lattice water at 90 ℃ and is stable below 500 ℃. Magnetic measurement reveals that 1 is a low-spin species in the range of 1.8~375 K.
Anew dinuclear cobalt(Ⅲ) complex, [Co2L3]·8H2O (1), (H2L=N，N'-bis(2-picolinoyl)hydrazine), was synthesized by a hydrothermal method and characterized by UV, FT-IR, ESI-MS, TGA, EA and single crystal X-ray crystallography. The complex crystallizes in trigonal system with space group R3c, a=1.63640(11) nm, α=48.52°, V=2.2556(3) nm3, Z=2, and final R=0.062. Each Co(Ⅲ) has an octahedral [CoN6] core. Each L2- ligand binds simultaneously to two Co(Ⅲ) cations in a bis(N，N')-bridging coordination mode with a Co…Co distance of 0.3497(2) nm. The hydrogen bonding interactions between carbonyl group and pyridyl ring link the molecules of 1 into a 1D chain which was further connected by the lattice water to form a 3D supramolecular framework. The TG analysis shows that 1 loses lattice water at 90 ℃ and is stable below 500 ℃. Magnetic measurement reveals that 1 is a low-spin species in the range of 1.8~375 K.
2014, 30(1): 169-178
doi: 10.11862/CJIC.2014.077
Abstract:
Modifying BODIPYwith a(4-hydroxyl)styryl group and a Zn2+ chelator respectively at α-and meso-positions resulted in a Zn2+ fluorescent sensor of yellow emission(580 nm) and large Stokes shift (~50 nm). The α-(4-hydroxyl)styryl-enhanced ICTeffect is responsible for the enlarged Stokes shift and bathochromic shifted excitation/emission of BODIPY, which favor to reduce the imaging interference of autofluorescence, phototoxicity and excitation. Photospectroscopic study disclosed the specific Zn2+-amplified fluorescence of this sensor, and the normal metal cations and near neutral pHshow very little interference to its Zn2+ sensing behavior. Its linear response range to Zn2+ is 0.12~1.2 μmol·L-1, and the LOD is 0.18 μmol·L-1. Confocal fluorescence imaging of intracellular Zn2+ in HeLa cells demonstrated the sensor's cell membrane permeability and its reversible cytosolic Zn2+ imaging ability.
Modifying BODIPYwith a(4-hydroxyl)styryl group and a Zn2+ chelator respectively at α-and meso-positions resulted in a Zn2+ fluorescent sensor of yellow emission(580 nm) and large Stokes shift (~50 nm). The α-(4-hydroxyl)styryl-enhanced ICTeffect is responsible for the enlarged Stokes shift and bathochromic shifted excitation/emission of BODIPY, which favor to reduce the imaging interference of autofluorescence, phototoxicity and excitation. Photospectroscopic study disclosed the specific Zn2+-amplified fluorescence of this sensor, and the normal metal cations and near neutral pHshow very little interference to its Zn2+ sensing behavior. Its linear response range to Zn2+ is 0.12~1.2 μmol·L-1, and the LOD is 0.18 μmol·L-1. Confocal fluorescence imaging of intracellular Zn2+ in HeLa cells demonstrated the sensor's cell membrane permeability and its reversible cytosolic Zn2+ imaging ability.
2014, 30(1): 179-184
doi: 10.11862/CJIC.2014.082
Abstract:
K2W3SeO12 was synthesized by hydrothermal method. It crystallizes in space group R3c of the rhombohedral system, with cell parameters a=b=c=1.25361(10) nm, α=β=γ=33.5390(10)°. It was further characterized by the tests of XRD, EDX, ATR-FTIR, UV-Vis-NIR, TGand SHG (second harmonic generation). Its powders show a phase-matchable SHG response of approximately 9 times of KDP. It also exhibits wide band gap (3.24 eV) and good thermal stability. Its infrared absorption wavelength can reach up to 10 μm. Therefore, K2W3SeO12 is regarded as a promising candidate for NLO (nonlinear optical) materials in the mid-IRregion.
K2W3SeO12 was synthesized by hydrothermal method. It crystallizes in space group R3c of the rhombohedral system, with cell parameters a=b=c=1.25361(10) nm, α=β=γ=33.5390(10)°. It was further characterized by the tests of XRD, EDX, ATR-FTIR, UV-Vis-NIR, TGand SHG (second harmonic generation). Its powders show a phase-matchable SHG response of approximately 9 times of KDP. It also exhibits wide band gap (3.24 eV) and good thermal stability. Its infrared absorption wavelength can reach up to 10 μm. Therefore, K2W3SeO12 is regarded as a promising candidate for NLO (nonlinear optical) materials in the mid-IRregion.
2014, 30(1): 185-191
doi: 10.11862/CJIC.2014.076
Abstract:
Highly dispersed SiO2 microspheres with mean diameter of 200 nm were prepared by modified Stöber method. Then the prepared SiO2 nanoparticles were coated with Co3O4 via liquid precipitation method and urea homogeneous precipitation method respectively, thus a new type SiO2/Co3O4 core-shell catalysts with different coating forms were obtained. X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared (IR) spectra, Raman Microscopy and BET specific surface area measurement were used to characterize the SiO2/Co3O4 composite nanoparticles. The catalytic activities of SiO2/Co3O4 composites for thermal decomposition of ammonium perchlorate (AP) were studied by differential scanning calorimetry (DSC). Furthermore, we espescially investigated the influence of different coating forms on its catalytic effect. The results indicate that SiO2/Co3O4 nanocomposites synthesised by different methods possess obvious core-shell structure are with high specific surface area,which are layer-coated and particle-coated respectively. And the catalytic activity of particle-coated SiO2/Co3O4 nanocomposites is best, which reduce the high decomposition temperature of AP by 110 ℃, and increase heat quantity by 662 J·g-1.
Highly dispersed SiO2 microspheres with mean diameter of 200 nm were prepared by modified Stöber method. Then the prepared SiO2 nanoparticles were coated with Co3O4 via liquid precipitation method and urea homogeneous precipitation method respectively, thus a new type SiO2/Co3O4 core-shell catalysts with different coating forms were obtained. X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared (IR) spectra, Raman Microscopy and BET specific surface area measurement were used to characterize the SiO2/Co3O4 composite nanoparticles. The catalytic activities of SiO2/Co3O4 composites for thermal decomposition of ammonium perchlorate (AP) were studied by differential scanning calorimetry (DSC). Furthermore, we espescially investigated the influence of different coating forms on its catalytic effect. The results indicate that SiO2/Co3O4 nanocomposites synthesised by different methods possess obvious core-shell structure are with high specific surface area,which are layer-coated and particle-coated respectively. And the catalytic activity of particle-coated SiO2/Co3O4 nanocomposites is best, which reduce the high decomposition temperature of AP by 110 ℃, and increase heat quantity by 662 J·g-1.
2014, 30(1): 192-203
doi: 10.11862/CJIC.2014.086
Abstract:
Six new 1D lanthanide-based coordination polymer helical chains with formulas of {[Ln(FINA)3(H2O)2]·H2O}n (Ln=Pr (1), Nd (2), Eu (3), Gd (4)), {[Dy(FINA)3(H2O)2]}n (5), and {[Gd(FINA)2(phen)(OH)]}n (6) (HFINA=2-Fluoroisonicotinic acid, phen=1,10-phenthroline), were synthesized and structurally characterized. It is the first time that 2-Fluoroisonicotinic acid is employed in producing coordination polymers. Carboxylate moieties of the ligand in these compounds exhibit two types of coordination modes because of the lanthanide contraction effect. Ln3+ ion is coordinated by eight donor atoms in a distorted bicapped trigonal-prismatic arrangement in 1~4 while in distorted dodecahedron geometry in 5~6. All of helical chains are further extended via the intermolecular π…π interactions, strong O-H…O/Nhydrogen bonds and C-H…F hydrogen bonds into a 3D supramolecular structures. Interestingly, in 1~4, there is a small 1D solvent channel along the b-axis, where water molecules are located. The luminescence properties of 3 and 4 have been investigated and the result indicate that compound 3 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion with a decay lifetime of 333.81 μs, while 4 would be attributed to the intraligand fluorescence, based on the emission spectrum of the free ligand. The magnetic properties of 2~6 reveal the weak antiferromagnetic characters. Additionally, the thermal analyses suggest the high thermal stability of compounds 1~6.
Six new 1D lanthanide-based coordination polymer helical chains with formulas of {[Ln(FINA)3(H2O)2]·H2O}n (Ln=Pr (1), Nd (2), Eu (3), Gd (4)), {[Dy(FINA)3(H2O)2]}n (5), and {[Gd(FINA)2(phen)(OH)]}n (6) (HFINA=2-Fluoroisonicotinic acid, phen=1,10-phenthroline), were synthesized and structurally characterized. It is the first time that 2-Fluoroisonicotinic acid is employed in producing coordination polymers. Carboxylate moieties of the ligand in these compounds exhibit two types of coordination modes because of the lanthanide contraction effect. Ln3+ ion is coordinated by eight donor atoms in a distorted bicapped trigonal-prismatic arrangement in 1~4 while in distorted dodecahedron geometry in 5~6. All of helical chains are further extended via the intermolecular π…π interactions, strong O-H…O/Nhydrogen bonds and C-H…F hydrogen bonds into a 3D supramolecular structures. Interestingly, in 1~4, there is a small 1D solvent channel along the b-axis, where water molecules are located. The luminescence properties of 3 and 4 have been investigated and the result indicate that compound 3 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion with a decay lifetime of 333.81 μs, while 4 would be attributed to the intraligand fluorescence, based on the emission spectrum of the free ligand. The magnetic properties of 2~6 reveal the weak antiferromagnetic characters. Additionally, the thermal analyses suggest the high thermal stability of compounds 1~6.
2014, 30(1): 204-212
doi: 10.11862/CJIC.2014.078
Abstract:
Three Co(Ⅱ) complexes based on E-3-[3-(carboxymethoxy)-phenyl]acrylic acid (H2L1) or E-3-[3-(carboxymethoxy)-phenyl]acrylic acid (H2L2), namely [Co(L1)(bpp)]n(1), {[Co(μ3-OH)2(L2)4(bpy)2(H2O)4]·12H2O}n (2), and [Co(L2)(bpy)]n(3) (bpp: 1,3-bi(pyridin-4-yl)propane, bpy: 4,4-bipyridine), were synthesized and characterized by elemental analysis, IR, XRPD and X-ray single-crystal structure analysis. Different coordination environment for Co(Ⅱ) ions and thereby different crystal structures and magnetism were observed for these three complexes. The magnetic properties of complexes 1 and 2 were discussed in detail.
Three Co(Ⅱ) complexes based on E-3-[3-(carboxymethoxy)-phenyl]acrylic acid (H2L1) or E-3-[3-(carboxymethoxy)-phenyl]acrylic acid (H2L2), namely [Co(L1)(bpp)]n(1), {[Co(μ3-OH)2(L2)4(bpy)2(H2O)4]·12H2O}n (2), and [Co(L2)(bpy)]n(3) (bpp: 1,3-bi(pyridin-4-yl)propane, bpy: 4,4-bipyridine), were synthesized and characterized by elemental analysis, IR, XRPD and X-ray single-crystal structure analysis. Different coordination environment for Co(Ⅱ) ions and thereby different crystal structures and magnetism were observed for these three complexes. The magnetic properties of complexes 1 and 2 were discussed in detail.
2014, 30(1): 213-219
doi: 10.11862/CJIC.2014.042
Abstract:
An efficient and facile aminobromination reaction of β-methyl-β-nitrostyrenes with PhCONH2/PhCONBr2 as nitrogen/bromine source has been developed, which could tolerate a wide scope of substrates with good chemical yield and diastereoselectivity. This aminobrominaiton system uses metal salt and base as the co-catalyst, which is different from our previous reported systems.
An efficient and facile aminobromination reaction of β-methyl-β-nitrostyrenes with PhCONH2/PhCONBr2 as nitrogen/bromine source has been developed, which could tolerate a wide scope of substrates with good chemical yield and diastereoselectivity. This aminobrominaiton system uses metal salt and base as the co-catalyst, which is different from our previous reported systems.
2014, 30(1): 220-226
doi: 10.11862/CJIC.2014.028
Abstract:
Deprotonated terephthalic acid (TA) and benzoic acid (BA), as sensitizers, were successfully intercalated into the layered terbium hydroxides, through ion-exchange reaction under hydrothermal condition. The photoluminescence spectra indicated that both of TA2- and BA- enhanced the characteristic green photolu-minescence emission of Tb3+ by the efficiency energy transition process between the sensitizer and Tb3+, and furthermore that the sensibilization of TA2- was much stronger than that of BA-. The mechanism of the energy transfer from the organic sensitizers to Tb3+ was discussed based on the energy level matching herein.
Deprotonated terephthalic acid (TA) and benzoic acid (BA), as sensitizers, were successfully intercalated into the layered terbium hydroxides, through ion-exchange reaction under hydrothermal condition. The photoluminescence spectra indicated that both of TA2- and BA- enhanced the characteristic green photolu-minescence emission of Tb3+ by the efficiency energy transition process between the sensitizer and Tb3+, and furthermore that the sensibilization of TA2- was much stronger than that of BA-. The mechanism of the energy transfer from the organic sensitizers to Tb3+ was discussed based on the energy level matching herein.
