Three new Zn（Ⅱ）/Cd（Ⅱ） coordination polymers based on 2-mercaptonicotinic acid （H2mna） with 1,2-di（4-pyridyl）ethylene （dpe） introduced as a bridging ligand have been synthesized via hydrothermal method and ...Three new Zn（Ⅱ）/Cd（Ⅱ） coordination polymers based on 2-mercaptonicotinic acid （H2mna） with 1,2-di（4-pyridyl）ethylene （dpe） introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2（dpe）0.5（mna）2] （1） can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn（Ⅱ） and mna ligands is bridged by dpe ligands, while the complex named [Zn4（dpe）4（mna）4] （2） is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C–H…π and π…π interactions. Compound 3 with general formular [Cd2（dpe）0.5（mna）2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd（Ⅱ） and mna ligands are connected with the bridging of dpe ligands.展开更多
A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-...A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.展开更多
Reducing 2, 6-pyridinedicaboxylic acid diethyl ester to 2,6-di(hydroxymethyl)pyridine was carried out by using NaBH4/CaCl2 as reducing agent. It is an improved and efficient method. The yield is up to 91%.
A 1-D paddle-wheel copper （Ⅱ） coordination polymer constructed by 2-nitrobenzene-1,4-di（oxyacetic） acid has been synthesized by hydrothermal reaction, and its crystal structure was determined by X-ray diffraction...A 1-D paddle-wheel copper （Ⅱ） coordination polymer constructed by 2-nitrobenzene-1,4-di（oxyacetic） acid has been synthesized by hydrothermal reaction, and its crystal structure was determined by X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 7.7257（12）, b = 8.3648（13）, c = 11.5516（18）A, α = 76.654（2）, β = 82.088（2）, γ = 63.636（2）°, C20H22Cu2N2O20, Mr = 737.48, V = 650.27（18）A^3, Dc = 1.883 g/cm^3, F（000） = 374,/1 = 1.737 cm^-1 and Z = 1. The final refinement gave R = 0.0345 and ωR = 0.0995 for 1996 observed reflections with I 〉 2σ（I）. The coordination polymer demonstrates a 1-D microporous structure, and the channel is formed by two NBDOA^2- and two Cu^2＋ ions. The ligand NBDOAH2 displays a good flexible characteristic. The 1-D chains are connected to a 3-D supramolecular network by hydrogen bonds.展开更多
The title complexes（NH4）[Ag（dpe）（H2bptc）]（1） and Ag2（bpy）（ox）·7H2O（2） were synthesized via slow evaporation at room temperature,and characterized by elemental analysis and infrared spectra.The cryst...The title complexes（NH4）[Ag（dpe）（H2bptc）]（1） and Ag2（bpy）（ox）·7H2O（2） were synthesized via slow evaporation at room temperature,and characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in triclinic,space group P1 with a = 8.3959（7）,b = 11.8088（12）,c = 12.8175（13） ,α = 85.507（2）,β = 79.245（1）,γ = 84.174（2）o,V = 1239.7（2） 3,Z = 2,C28H22AgN3O8,Mr = 636.36,Dc = 1.705 g/cm3,F（000） = 644 and μ（MoKα） = 0.874 mm-1.The final R = 0.0479 and wR = 0.1426 for 3632 observed reflections with I 〉2σ（I） and R = 0.0559 and wR = 0.1503 for all data.The crystal of 2 crystallizes in orthorhombic,space group Pnna with a = 17.2291（17）,b = 7.5289（6）,c = 21.369（2）,V = 2771.9（4） 3,Z = 4,C22H30Ag2N4O11,Mr = 742.24,Dc = 1.779 g/cm3,F（000） = 1488 and μ（MoKα） = 1.476 mm-1.The final R = 0.0648 and wR = 0.2058 for 1996 observed reflections with I 〉2σ（I） and R = 0.0769 and wR = 0.2192 for all data.X-ray diffraction reveals that in complexes 1 and 2,both 1,2-di（4-pyridyl）ethylene and 4,4＇-bipyridine act as typical bidentate N-donor ligands to link two Ag centers.3,3＇4,4＇-Biphenyltetracarboxylate and oxalate anions play the role of organic linkers and counter-ions to balance the cationic charge of AgI.The rich hydrogen-bonding interactions and ligand-unsupported Ag…Ag interactions as well as π-π stacking interactions contribute to the construction of three-dimensional sandwich-like frameworks.展开更多
Furan carboxylic acids are important building blocks in polymer and fine chemical industries. In this work, a simple substrate adaptation strategy was applied to improve the catalytic performances of Comamonas testost...Furan carboxylic acids are important building blocks in polymer and fine chemical industries. In this work, a simple substrate adaptation strategy was applied to improve the catalytic performances of Comamonas testosteroni SC1588 cells for the synthesis of various furan carboxylic acids. It was found that biocatalytic synthesis of 5-hydroxymethyl-2-furancarboxylic acid(HMFCA) was substantially promoted by adding histidine and increasing cell concentrations. HMFCA was produced in a quantitative yield from200 m M HMF in 24 h. Besides, the HMFCA yields of 71%–81% were achieved with the substrate concentrations up to 250–300 m M. It was firstly found that 4-tert-butylcatechol(TBC), as the stabilizer present in HMF, exerted a significantly detrimental effect on whole-cell catalytic synthesis of HMFCA at high substrate concentrations(more than 130 m M). In addition, a variety of furan carboxylic acids such as2-furoic acid, 5-methyl-2-furancarboxylic acid and 5-methoxymethyl-2-furancarboxylic acid were synthesized with the yields up to 98%.展开更多
基金supported by grants from the 973 Program(2012CB821702)the National Natural Science Foundation of China(21073192,21173223 and 21173220)the Science Foundation of CAS(KJCX2-YW-H20)and of Fujian Province(2009HZ0006-1)
文摘Three new Zn（Ⅱ）/Cd（Ⅱ） coordination polymers based on 2-mercaptonicotinic acid （H2mna） with 1,2-di（4-pyridyl）ethylene （dpe） introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2（dpe）0.5（mna）2] （1） can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn（Ⅱ） and mna ligands is bridged by dpe ligands, while the complex named [Zn4（dpe）4（mna）4] （2） is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C–H…π and π…π interactions. Compound 3 with general formular [Cd2（dpe）0.5（mna）2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd（Ⅱ） and mna ligands are connected with the bridging of dpe ligands.
基金supported by the National Natural Science Foundation of China(Nos.21571118&21271121)
文摘A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.
文摘Reducing 2, 6-pyridinedicaboxylic acid diethyl ester to 2,6-di(hydroxymethyl)pyridine was carried out by using NaBH4/CaCl2 as reducing agent. It is an improved and efficient method. The yield is up to 91%.
基金the National Natural Science Foundation of China (No.20471008)the Excellent Young Scholars Research Fund of Beijing Institute of Technology (No.000Y02-8)
文摘A 1-D paddle-wheel copper （Ⅱ） coordination polymer constructed by 2-nitrobenzene-1,4-di（oxyacetic） acid has been synthesized by hydrothermal reaction, and its crystal structure was determined by X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 7.7257（12）, b = 8.3648（13）, c = 11.5516（18）A, α = 76.654（2）, β = 82.088（2）, γ = 63.636（2）°, C20H22Cu2N2O20, Mr = 737.48, V = 650.27（18）A^3, Dc = 1.883 g/cm^3, F（000） = 374,/1 = 1.737 cm^-1 and Z = 1. The final refinement gave R = 0.0345 and ωR = 0.0995 for 1996 observed reflections with I 〉 2σ（I）. The coordination polymer demonstrates a 1-D microporous structure, and the channel is formed by two NBDOA^2- and two Cu^2＋ ions. The ligand NBDOAH2 displays a good flexible characteristic. The 1-D chains are connected to a 3-D supramolecular network by hydrogen bonds.
基金Supported by the National Natural Science Foundation of China (No. 20875007)Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (No. PHR201008372 and PHR201106124)the Research Fund of Beijing University of Civil Engineering and Architecture (No. 100902602)
文摘The title complexes（NH4）[Ag（dpe）（H2bptc）]（1） and Ag2（bpy）（ox）·7H2O（2） were synthesized via slow evaporation at room temperature,and characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in triclinic,space group P1 with a = 8.3959（7）,b = 11.8088（12）,c = 12.8175（13） ,α = 85.507（2）,β = 79.245（1）,γ = 84.174（2）o,V = 1239.7（2） 3,Z = 2,C28H22AgN3O8,Mr = 636.36,Dc = 1.705 g/cm3,F（000） = 644 and μ（MoKα） = 0.874 mm-1.The final R = 0.0479 and wR = 0.1426 for 3632 observed reflections with I 〉2σ（I） and R = 0.0559 and wR = 0.1503 for all data.The crystal of 2 crystallizes in orthorhombic,space group Pnna with a = 17.2291（17）,b = 7.5289（6）,c = 21.369（2）,V = 2771.9（4） 3,Z = 4,C22H30Ag2N4O11,Mr = 742.24,Dc = 1.779 g/cm3,F（000） = 1488 and μ（MoKα） = 1.476 mm-1.The final R = 0.0648 and wR = 0.2058 for 1996 observed reflections with I 〉2σ（I） and R = 0.0769 and wR = 0.2192 for all data.X-ray diffraction reveals that in complexes 1 and 2,both 1,2-di（4-pyridyl）ethylene and 4,4＇-bipyridine act as typical bidentate N-donor ligands to link two Ag centers.3,3＇4,4＇-Biphenyltetracarboxylate and oxalate anions play the role of organic linkers and counter-ions to balance the cationic charge of AgI.The rich hydrogen-bonding interactions and ligand-unsupported Ag…Ag interactions as well as π-π stacking interactions contribute to the construction of three-dimensional sandwich-like frameworks.
基金financially supported by the National Natural Science Foundation of China(21676103)the Natural Science Foundation of Guangdong Province(2017A030313056)the Science and Technology Project of Guangzhou City(201804010179)。
文摘Furan carboxylic acids are important building blocks in polymer and fine chemical industries. In this work, a simple substrate adaptation strategy was applied to improve the catalytic performances of Comamonas testosteroni SC1588 cells for the synthesis of various furan carboxylic acids. It was found that biocatalytic synthesis of 5-hydroxymethyl-2-furancarboxylic acid(HMFCA) was substantially promoted by adding histidine and increasing cell concentrations. HMFCA was produced in a quantitative yield from200 m M HMF in 24 h. Besides, the HMFCA yields of 71%–81% were achieved with the substrate concentrations up to 250–300 m M. It was firstly found that 4-tert-butylcatechol(TBC), as the stabilizer present in HMF, exerted a significantly detrimental effect on whole-cell catalytic synthesis of HMFCA at high substrate concentrations(more than 130 m M). In addition, a variety of furan carboxylic acids such as2-furoic acid, 5-methyl-2-furancarboxylic acid and 5-methoxymethyl-2-furancarboxylic acid were synthesized with the yields up to 98%.
