The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR,...The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR, IR, FAB-MS.展开更多
A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesi...A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.展开更多
Hydrothermal treatment of MCl2 ( M = Co or Cu ) , NH4 VO3, and 1,10-phenanthroline-5,6-dione (pdon) resulted in the formation of a duplex coordination polymer [ Co ( bpdc ) ( H2O ) 3 ] · H2O ( bpdc = 2,2...Hydrothermal treatment of MCl2 ( M = Co or Cu ) , NH4 VO3, and 1,10-phenanthroline-5,6-dione (pdon) resulted in the formation of a duplex coordination polymer [ Co ( bpdc ) ( H2O ) 3 ] · H2O ( bpdc = 2,2'-bipyridine-3,3'-dicarboxylate) and a chain-like coordination polymer [ Cu (bpy) V2O6 ] ( bpy = 2,2'-bipyridine ). X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed.展开更多
Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien,...Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13) and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.展开更多
A series of substituted chiral benzhydrols were synthesized by the reaction of aromatic aldehydes with chiral intermediates formed from chiral titanates and arylmagnesium halides.
The effects of the chain length and stereo-factor of substrates and solvents on the lipase catalysed lactonization of ω-hydroxy-ester were studied, And also the catalytic effects of various enzymes were compared.
l,2-Bis(2,2'-bipyridinyl)ethylene(1) ligand was synthesized by Wittig-Horner reaction and 1, 2-Bis(2, 2'-bipyridinyl)ethane(2) ligand(which can be obtained via another route ) was prepared by hydrogenation of ...l,2-Bis(2,2'-bipyridinyl)ethylene(1) ligand was synthesized by Wittig-Horner reaction and 1, 2-Bis(2, 2'-bipyridinyl)ethane(2) ligand(which can be obtained via another route ) was prepared by hydrogenation of (1). The formation of complexes of (1) and (2) with copper (I) has been studied. The influence of the different bridge chains (CH =CH, CH2CH2) on complexation is discussed on the basis of 1H NMR spectra. Keywords Dipyridine aldehyde, Dipyridine derivative, Copper complex展开更多
The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, (H6BDBPH)Br6·4H2O (C 26H 56N6O6Br6, Mr= 1028.23), crystallizes in the monoclinic system, space group P21/c, with cell par...The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, (H6BDBPH)Br6·4H2O (C 26H 56N6O6Br6, Mr= 1028.23), crystallizes in the monoclinic system, space group P21/c, with cell parameters: a=14.441(5), b=11.482(4), c=12.090(6), β=96.92°, V= 1990 (1)3, Z=2, Dc=1.716 g/cm3; F(000) =1024. MoKα radiation, λ= 0.71013), R = 0.0643 and wR = 0.1356 for 3507 independent reflections with I>2σ(I). The macrocyclic ligand adapts chair form, and the crystallographic inversion center is located in the macrocyclic cavity, and the six bromide ions and four water molecules are situated symmetrically outside the macrocyclic cavity.展开更多
Starting from podophyllotoxin, five new derivatives with macrocyclic dilactone 5 similar to 9 have been synthesized,and their structures were confirmed by IR, MS,H-1 NMR as well as HRMS. The key step is cyclization by...Starting from podophyllotoxin, five new derivatives with macrocyclic dilactone 5 similar to 9 have been synthesized,and their structures were confirmed by IR, MS,H-1 NMR as well as HRMS. The key step is cyclization by high dilution method.展开更多
The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG an...The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a=33.061(4), b=15.3457(17), c=33.902(4), β=101.930(2)°, Mr=4904.08, V=16828(3)3 , Z=4, Dc=1.936 g/cm3 , F(000)=9832, μ=2.425 mm-1 , the final R=0.0402 and wR=0.0969. The mixed valence vanadium clusters of [V34O82]10- bridges [NiL]2+ to form a one-dimensional chain in 1. To the best of our knowledge, the title complex is the first example of organic-inorganic hybrid material involving the largest vanadium cluster of [V34O82]10-.展开更多
The rational design and synthesis of metal-directed supramolecular framework compounds have received much attention in coordination chemistry because of their potential applications in catalysis, molecular selection, ...The rational design and synthesis of metal-directed supramolecular framework compounds have received much attention in coordination chemistry because of their potential applications in catalysis, molecular selection, nonlinear optics, ion exchange, and microelectronics. Many high-dimensional coordination complexes have been designed and prepared through molecular self-assembly processes. The open metal organic framework can be produced via two kinds of interactions, i. e. , coordinate covalent bonds and weaker intermolecular forces. For this reason, the most efficient means to synthesize these compounds is to establish possible connections among different units.展开更多
A new dimeric lanthanum (Ⅲ) complex [La_2(phen)_2(C_7H_3N_2O_6)_6] (phen=1, 10-phenanthroline) was synthesized by the hydrothermal method and determined by single crystal X-ray diffraction analysis. The La(Ⅲ) ion is...A new dimeric lanthanum (Ⅲ) complex [La_2(phen)_2(C_7H_3N_2O_6)_6] (phen=1, 10-phenanthroline) was synthesized by the hydrothermal method and determined by single crystal X-ray diffraction analysis. The La(Ⅲ) ion is coordinated to seven oxygen atoms from five carboxylate groups and two nitrogen atoms from a phen ligand, forming a monocapped square antiprismatic geometry. Six carboxylate groups coordinate to two La(Ⅲ) ions in three modes which are chelating bidentate, bridging bidentate and bridging tridentate. The crystal is triclinic with space group P-1, a=1.2030(4) nm, b=1.2962(5) nm, c=1.3330(5) nm, α=104.410(5)°, β=114.048(4)°, γ=100.054 (4)°, V=1.7467 (10) nm^3, M_r=952.46, Z=2, D_c=1.811 g·cm^(-3), F(000)=944, S=1.017, μ=1.320 mm^(-1), with R1=0.0298 and wR2=0.0625.展开更多
An improved procedure was used to prepare the asymmetric tripyrrane-containing macrocycles, The yield was over 85% These maerocycles could be oxidized to the methine bridled 23 (?)-electron aromatic cadmium(Ⅱ)complex...An improved procedure was used to prepare the asymmetric tripyrrane-containing macrocycles, The yield was over 85% These maerocycles could be oxidized to the methine bridled 23 (?)-electron aromatic cadmium(Ⅱ)complexes by reating with cadmium chloride in the presence of air and their atructures were characterized.展开更多
metol-free Robson -type macrocycle was synthesized for first time by proton-templation and from that the metal complexes were prepared.By X-ray study the structure of Ni(Ⅱ)-complex was characterized.
Monodispersed dihydrated zinc oxalate(ZnC_2O_4·2H_2O) particles with characteristic morphology were synthesized by aging a mixed solution of zinc nitrate(Zn(NO_3)_2) and sodium oxalate(Na_2C_2O_4) in the presence...Monodispersed dihydrated zinc oxalate(ZnC_2O_4·2H_2O) particles with characteristic morphology were synthesized by aging a mixed solution of zinc nitrate(Zn(NO_3)_2) and sodium oxalate(Na_2C_2O_4) in the presence of a citrate ligand, with an average flat size of approximately 10–15 μm. The important parameters, including the solution pH values and the concentration of the zinc ions and citrate ligand, were investigated using a series of experiments. It is verified that the citrate ligand significantly affects the morphology of zinc oxalate particles, probably via its multiple roles of chelating, dispersing, and selective absorption. Thermodynamic equilibrium of the distribution of zinc species in an aqueous solution of Zn(Ⅱ)-citrate-oxalate-H_2O was estimated to explain the experimental results and to clarify the size and morphological evolution mechanism of the precipitated particles.展开更多
The electro-catalytic properties can be effectively optimized by designing bimetallic alloy nanoparticles with high-content less-active metal to enhance the competence of more-active noble metal. Herein, a one-pot hyd...The electro-catalytic properties can be effectively optimized by designing bimetallic alloy nanoparticles with high-content less-active metal to enhance the competence of more-active noble metal. Herein, a one-pot hydrothermal approach is demonstrated for the controllable synthesis of Ag-rich Ag_9Pd_1 alloy nanoactiniae with obviously enhanced electro-catalytic activity(2.23 mA cm^(-2) at 0.85 V) and stability for oxygen reduction reaction. In alkaline solution, the ORR onset potential and half-wave potential of the Ag_9Pd_1 alloy nanoactiniae can reach a value of 1.02 V and 0.89 V, respectively, which origin from strong ligand and ensemble effects between Pd element and Ag element. The nanocrystals are uniformly alloyed, displaying a Ag_9Pd_1 combination, as displayed by an assembly of X-ray diffraction(XRD) spectrum,energy dispersive X-ray(EDX) analysis, and cyclic voltammetry(CV). This concept of tuning bimetallic alloy nanocrystals with low concentrations of more precious metal may be a promising approach to be applicable to a wide range of alloy nanocrystals.展开更多
A novel macrocycle containing thiophene (L) was prepared first by the interaction of 2,5-bis-(chloromethyl)-thiophene (A) and salicylaldehyde to give 2, 5-bis-(2-formylphenoxymethyl)-thiophene (B), and then ...A novel macrocycle containing thiophene (L) was prepared first by the interaction of 2,5-bis-(chloromethyl)-thiophene (A) and salicylaldehyde to give 2, 5-bis-(2-formylphenoxymethyl)-thiophene (B), and then by the nontemplate cyclocondensation of 1,3-diaminopropane with (B) followed by a "onepot" reduction without isolation of the diimine intermediate. The corresponding silver complex, AgLClO;, was also prepared. The macrocycle was characterized by IR, elemental analysis, MS and;HNMR.展开更多
文摘The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR, IR, FAB-MS.
文摘A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.
基金Supported by Natural Science Foundation of Liaoning Province(No20061073)Education Committee Foundation of Liao-ning Province(No2004F023)
文摘Hydrothermal treatment of MCl2 ( M = Co or Cu ) , NH4 VO3, and 1,10-phenanthroline-5,6-dione (pdon) resulted in the formation of a duplex coordination polymer [ Co ( bpdc ) ( H2O ) 3 ] · H2O ( bpdc = 2,2'-bipyridine-3,3'-dicarboxylate) and a chain-like coordination polymer [ Cu (bpy) V2O6 ] ( bpy = 2,2'-bipyridine ). X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed.
基金supported by the National Natural Science Foundation of China(No.20771083)
文摘Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13) and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.
文摘A series of substituted chiral benzhydrols were synthesized by the reaction of aromatic aldehydes with chiral intermediates formed from chiral titanates and arylmagnesium halides.
文摘The effects of the chain length and stereo-factor of substrates and solvents on the lipase catalysed lactonization of ω-hydroxy-ester were studied, And also the catalytic effects of various enzymes were compared.
文摘l,2-Bis(2,2'-bipyridinyl)ethylene(1) ligand was synthesized by Wittig-Horner reaction and 1, 2-Bis(2, 2'-bipyridinyl)ethane(2) ligand(which can be obtained via another route ) was prepared by hydrogenation of (1). The formation of complexes of (1) and (2) with copper (I) has been studied. The influence of the different bridge chains (CH =CH, CH2CH2) on complexation is discussed on the basis of 1H NMR spectra. Keywords Dipyridine aldehyde, Dipyridine derivative, Copper complex
文摘The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, (H6BDBPH)Br6·4H2O (C 26H 56N6O6Br6, Mr= 1028.23), crystallizes in the monoclinic system, space group P21/c, with cell parameters: a=14.441(5), b=11.482(4), c=12.090(6), β=96.92°, V= 1990 (1)3, Z=2, Dc=1.716 g/cm3; F(000) =1024. MoKα radiation, λ= 0.71013), R = 0.0643 and wR = 0.1356 for 3507 independent reflections with I>2σ(I). The macrocyclic ligand adapts chair form, and the crystallographic inversion center is located in the macrocyclic cavity, and the six bromide ions and four water molecules are situated symmetrically outside the macrocyclic cavity.
文摘Starting from podophyllotoxin, five new derivatives with macrocyclic dilactone 5 similar to 9 have been synthesized,and their structures were confirmed by IR, MS,H-1 NMR as well as HRMS. The key step is cyclization by high dilution method.
基金supported by the Science and Technology Planning Project of Hunan Province (2012FJ3050, 2012NK3067)the Construct Program of the Key Discipline in Hunan Province (2011–76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province (2012–318)
文摘The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a=33.061(4), b=15.3457(17), c=33.902(4), β=101.930(2)°, Mr=4904.08, V=16828(3)3 , Z=4, Dc=1.936 g/cm3 , F(000)=9832, μ=2.425 mm-1 , the final R=0.0402 and wR=0.0969. The mixed valence vanadium clusters of [V34O82]10- bridges [NiL]2+ to form a one-dimensional chain in 1. To the best of our knowledge, the title complex is the first example of organic-inorganic hybrid material involving the largest vanadium cluster of [V34O82]10-.
基金Supported by the Education Office of Jilin Province of China(No 0047)
文摘The rational design and synthesis of metal-directed supramolecular framework compounds have received much attention in coordination chemistry because of their potential applications in catalysis, molecular selection, nonlinear optics, ion exchange, and microelectronics. Many high-dimensional coordination complexes have been designed and prepared through molecular self-assembly processes. The open metal organic framework can be produced via two kinds of interactions, i. e. , coordinate covalent bonds and weaker intermolecular forces. For this reason, the most efficient means to synthesize these compounds is to establish possible connections among different units.
文摘A new dimeric lanthanum (Ⅲ) complex [La_2(phen)_2(C_7H_3N_2O_6)_6] (phen=1, 10-phenanthroline) was synthesized by the hydrothermal method and determined by single crystal X-ray diffraction analysis. The La(Ⅲ) ion is coordinated to seven oxygen atoms from five carboxylate groups and two nitrogen atoms from a phen ligand, forming a monocapped square antiprismatic geometry. Six carboxylate groups coordinate to two La(Ⅲ) ions in three modes which are chelating bidentate, bridging bidentate and bridging tridentate. The crystal is triclinic with space group P-1, a=1.2030(4) nm, b=1.2962(5) nm, c=1.3330(5) nm, α=104.410(5)°, β=114.048(4)°, γ=100.054 (4)°, V=1.7467 (10) nm^3, M_r=952.46, Z=2, D_c=1.811 g·cm^(-3), F(000)=944, S=1.017, μ=1.320 mm^(-1), with R1=0.0298 and wR2=0.0625.
文摘An improved procedure was used to prepare the asymmetric tripyrrane-containing macrocycles, The yield was over 85% These maerocycles could be oxidized to the methine bridled 23 (?)-electron aromatic cadmium(Ⅱ)complexes by reating with cadmium chloride in the presence of air and their atructures were characterized.
文摘metol-free Robson -type macrocycle was synthesized for first time by proton-templation and from that the metal complexes were prepared.By X-ray study the structure of Ni(Ⅱ)-complex was characterized.
文摘Monodispersed dihydrated zinc oxalate(ZnC_2O_4·2H_2O) particles with characteristic morphology were synthesized by aging a mixed solution of zinc nitrate(Zn(NO_3)_2) and sodium oxalate(Na_2C_2O_4) in the presence of a citrate ligand, with an average flat size of approximately 10–15 μm. The important parameters, including the solution pH values and the concentration of the zinc ions and citrate ligand, were investigated using a series of experiments. It is verified that the citrate ligand significantly affects the morphology of zinc oxalate particles, probably via its multiple roles of chelating, dispersing, and selective absorption. Thermodynamic equilibrium of the distribution of zinc species in an aqueous solution of Zn(Ⅱ)-citrate-oxalate-H_2O was estimated to explain the experimental results and to clarify the size and morphological evolution mechanism of the precipitated particles.
基金sponsored by the National Natural Science Foundation of China (21576139, 21503111)the Natural Science Foundation of Jiangsu Province (BK20171473)+1 种基金the National and Local Joint Engineering Research Center of Biomedical Functional Materials, Natural Science Foundation of Jiangsu Higher Education Institutions of China (16KJB150020)a project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The electro-catalytic properties can be effectively optimized by designing bimetallic alloy nanoparticles with high-content less-active metal to enhance the competence of more-active noble metal. Herein, a one-pot hydrothermal approach is demonstrated for the controllable synthesis of Ag-rich Ag_9Pd_1 alloy nanoactiniae with obviously enhanced electro-catalytic activity(2.23 mA cm^(-2) at 0.85 V) and stability for oxygen reduction reaction. In alkaline solution, the ORR onset potential and half-wave potential of the Ag_9Pd_1 alloy nanoactiniae can reach a value of 1.02 V and 0.89 V, respectively, which origin from strong ligand and ensemble effects between Pd element and Ag element. The nanocrystals are uniformly alloyed, displaying a Ag_9Pd_1 combination, as displayed by an assembly of X-ray diffraction(XRD) spectrum,energy dispersive X-ray(EDX) analysis, and cyclic voltammetry(CV). This concept of tuning bimetallic alloy nanocrystals with low concentrations of more precious metal may be a promising approach to be applicable to a wide range of alloy nanocrystals.
基金This project is supported by the National Natural Science Foundation of China.
文摘A novel macrocycle containing thiophene (L) was prepared first by the interaction of 2,5-bis-(chloromethyl)-thiophene (A) and salicylaldehyde to give 2, 5-bis-(2-formylphenoxymethyl)-thiophene (B), and then by the nontemplate cyclocondensation of 1,3-diaminopropane with (B) followed by a "onepot" reduction without isolation of the diimine intermediate. The corresponding silver complex, AgLClO;, was also prepared. The macrocycle was characterized by IR, elemental analysis, MS and;HNMR.