A coordination polymer [Co(dpa)prz0.5]n(1) with double-helix chains has been constructed hydrothermally using H2dpa(H2dpa=diphenic acid),prz(prz=piperazine) and Co(NO3)2.6H2O.The structure and magnetic properties of t...A coordination polymer [Co(dpa)prz0.5]n(1) with double-helix chains has been constructed hydrothermally using H2dpa(H2dpa=diphenic acid),prz(prz=piperazine) and Co(NO3)2.6H2O.The structure and magnetic properties of the complex were investigated.The complex crystallizes in triclinic system and P1 space group.Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry.Two carboxylates of the H2dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical-C-O-Co-chains.The two types of helical chains are interconnected to each other through the Co (Ⅱ) centers to produce double-helix chains.The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains.The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks.Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions.展开更多
A new 3D complex,[Co（L）（bpe）0.5（H2O）2]n（1,H2 L = 5-iodo-benzene-1,3-dioxyacetic acid,bpe = 1,2-bis（4-pyridyl）ethylene）,has been hydrothermally synthesized and structurally characterized by elemental analysis...A new 3D complex,[Co（L）（bpe）0.5（H2O）2]n（1,H2 L = 5-iodo-benzene-1,3-dioxyacetic acid,bpe = 1,2-bis（4-pyridyl）ethylene）,has been hydrothermally synthesized and structurally characterized by elemental analysis,IR and X-ray diffraction.It is formulated as C16H16 Co INO8,crystallizes in monoclinic,space group P21/c,with a = 9.806（2）,b = 6.5492（13）,c = 28.187（8） A,β = 100.12（3）°,V = 1782.0（7） A^3,Z = 4,Dc = 1.998 g/m^3,F（000） = 1052,Μr = 536.13,the final R = 0.0393 and w R = 0.0858 for 3134 observed reflections with I 〉 2σ（I）.Complex 1 displays a 3D framework with multiform helical features,left-and right-handed triple helical braids and single helical chains,which can be simplified as a new type of（3,4）-connected lattice with a（6·10^2）（6^2·10^4） SchlAfli symbol.Moreover,the thermal analysis of complex 1 has also been investigated.展开更多
An air and moisture stable ruthenium（Ⅲ） formate complex[Ru（HCO2）Cl2]n has been synthesized and examined in the epoxidation of substituted styrenes.X-ray crystallographic data of this complex were determined and s...An air and moisture stable ruthenium（Ⅲ） formate complex[Ru（HCO2）Cl2]n has been synthesized and examined in the epoxidation of substituted styrenes.X-ray crystallographic data of this complex were determined and showed that the formate ligand coordinates to the ruthenium centers in a μ~2-η~2 fashion（syn,syn）.Its asymmetric unit contains one Ru（Ⅲ） ion together with the half of a formate ligand and one chloride anion,which are bridged between the metal centers,forming a 1-D chain coordination polymer.This electron deficient helical coordination polymer was employed in the epoxidation of parafluorostyrene,affording the epoxide product in 92%yield.Natural chirality of this coordination polymer is applicable in asymmetric epoxidation reactions.展开更多
Three novel enantiopure phenyl isocyanide monomers with BH3-protected phosphine functional group were designed and synthesized. Polymerization of these monomers using a alkyne-Pd（II） complex as a catalyst led to the...Three novel enantiopure phenyl isocyanide monomers with BH3-protected phosphine functional group were designed and synthesized. Polymerization of these monomers using a alkyne-Pd（II） complex as a catalyst led to the formation of respective helical polyisocyanides in high yields with controlled molecular weights（Mns） and narrow molecular weight distributions（Mw/Mns）. Removing the protecting BH3 groups afforded helical poly（phenyl isocyanide）s bearing phosphine pendants. Thanks to the chiral induction of monomer, the isolated helical polyisocyanides showed high optical activity, as revealed by circular dichroism（CD） and absorption spectroscopies and polarimetry. The helical structures of these polymers were quite stable in various organic solvents with different polarities and in a wide temperature range. Moreover, these helical polymers could be used as organocatalysts and showed good performance in enantioselective cross Rauhut-Currier reaction. The enantiomeric excess（ee） values of the isolated products of cross Rauhut-Currier reaction could be up to 90%. The polymer organocatalysts could be easily recovered from the reaction mixtures and reused at least five times in the reaction without significant loss of their enantioselectivities and catalytic activities.展开更多
Two novel coordination polymers with helical chains, {[Zn（L）（H2O）]·H2O}n（1） and {[Zn（L）（p-bix）]·3.5H2O}n（2）, where H2 L = 5-（4-hydroxypyridinium-1-ylmethyl） isophthalic acid and p-bix = 1,4-bis...Two novel coordination polymers with helical chains, {[Zn（L）（H2O）]·H2O}n（1） and {[Zn（L）（p-bix）]·3.5H2O}n（2）, where H2 L = 5-（4-hydroxypyridinium-1-ylmethyl） isophthalic acid and p-bix = 1,4-bis（imidazol-1-ylmethyl）benzene, have been hydrothermally synthesized, and charac-terized by elemental analysis, powder X-ray diffraction（PXRD）, IR, thermal gravimetric analyses（TGA） and also by single-crystal X-ray diffraction. Both complexes 1 and 2 crystallize inmonoclinic, space group P21/c. Compound 1 displays a two-dimensional（2D） structure with two distinct types of helical chains; 2 shows a layered coordination polymer with two types of helical chains and features an interesting 2D→3D interdigitated architecture. Meanwhile, the luminescent properties of 1 and 2 have also been investigated in detail.展开更多
A novel manganese（Ⅱ） coordination polymer with 2-（4-carboxyphenoxy） benzoic acid （2,4＇-H2oba） and 1,10-phenanthroline （1,10-phen） has been prepared by hydrothermal synthesis and characterized by single-cryst...A novel manganese（Ⅱ） coordination polymer with 2-（4-carboxyphenoxy） benzoic acid （2,4＇-H2oba） and 1,10-phenanthroline （1,10-phen） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and elemental analysis. Compound [Mn（2,4＇-oba）（1,10-phen）] is of monoclinic system, space group P21/n with a = 7.960（1）, b = 15.464（2）, c = 18.703（3）A, β = 99.976（2）°, V = 2267.5（6） A^3, Z = 4, Mr = 491.35, Dc = 1.439 g/cm^3, F（000） = 1004 and μ = 0.623 cm·1. The final R = 0.0419 and wR = 0.0978 for 3444 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the oba2-ligands adopt a bis（chelating bidentate） mode to link two Mn（Ⅱ） centers to form an infinite 1D helical chain. Furthermore, a 3D supramolecular structure was formed by π-π stacking interactions and hydrogen bonds.展开更多
Two novel 2D coordination polymers, [Co（BPDC）DMSO]·DMSO（1）（BPDC=2,2＇-bipyridyl-4,4＇-dicar- boxylic acid） and [Zn（BPDC）DMF]·DMF（2）, were synthesized from 2,2＇-bipyridyl-4,4＇-dicarboxylic acid li...Two novel 2D coordination polymers, [Co（BPDC）DMSO]·DMSO（1）（BPDC=2,2＇-bipyridyl-4,4＇-dicar- boxylic acid） and [Zn（BPDC）DMF]·DMF（2）, were synthesized from 2,2＇-bipyridyl-4,4＇-dicarboxylic acid ligand （H2BPDC） under solvothermal conditions. Single crystal X-ray diffraction analyses reveal that compound 1 crystal- lizes in orthorhombic system and Pca21 space group with a=1.29628（13） nm, b=1.13721（13） nm, c=1.66457（19） nm, α=90°, β=90°, γ=90°, V=2.4538（5） nm3. Compound 2 crystallizes in monoclinic system and P21/c space group with a=0.9429（6） nm, b=1.4757（10） nm, c=1.5980（9） nm, α=90°, β=114°, γ=90°, V=2.030（2） nm3. Compounds 1 and 2 exhibit two different 3-connected hcb and fes topologies, respectively. The structures of the two compounds both contain interesting characters of double-helical chains（left- and right-handed helical chains）. Additionally, the mag- netic and luminescent properties of the two compounds were studied.展开更多
A new AgO） coordination polymer, {[Ag（1,3-BIP）（H20）][Ag（1,3- BIP）（PMA）0.5.- 4H20}n （PMA = 1,2,4,5-benzenetricarboxylic acid, 1,3-BIP = 1,3-bis（imidazole）propane）, have been synthesized and characterized b...A new AgO） coordination polymer, {[Ag（1,3-BIP）（H20）][Ag（1,3- BIP）（PMA）0.5.- 4H20}n （PMA = 1,2,4,5-benzenetricarboxylic acid, 1,3-BIP = 1,3-bis（imidazole）propane）, have been synthesized and characterized by single-crystal X-ray diffraction, powder XRD, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that the title complex is formed by 1D polymeric cationic chains of [Ag（1,3-BIP）（H2O）]n^n＋ and 2D polymetric anionic layer of [Ag（1,3-BIP）（PMA）0.5]n^n-, which are further linked by intermolecular H-bonding to form a 3D supramolecular framework. In addition, the photoluminescence property of the title complex in the solid state at room temperature was also investigated.展开更多
5-（Hydroxymethyl） isophthalic acid （H2HIA） as a novel organic ligand was prepared from 3,5-bis（methoxycarbonyl）benzoic acid by a two-step method. And then, a 3D helical coor- dination polymer with a 3-fold inter...5-（Hydroxymethyl） isophthalic acid （H2HIA） as a novel organic ligand was prepared from 3,5-bis（methoxycarbonyl）benzoic acid by a two-step method. And then, a 3D helical coor- dination polymer with a 3-fold interpenetration structure, namely [Zn1/2（HIA）1/2（DPEE）1/2]n （1）, was hydrothermally synthesized at 160 ℃, using H2HIA ligands to assemble with DPEE ligands and Zn2＋ ions. Complex 1 crystalizes in orthorhombic system, space group Pnna, with a = 8.2118（5）, b = 17.1698（7）, c =14.9922（7） ？, V = 2113.82（18） ？3, μ = 1.194 mm-1, Z = 4 and S = 0.967. Moreover, some physical characteristics of complex 1, such as powder X-ray diffraction （PXRD）, thermogravimetry analyses （TGA） and photoluminescent properties, were also investigated.展开更多
One new chiral metal-organic coordination polymer,[Cd2（dpb）（H2hfipbb）2]n,was obtained under hydrothermal conditions of 1,3-di（pyridineyl）benzene（dpb） and 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）（...One new chiral metal-organic coordination polymer,[Cd2（dpb）（H2hfipbb）2]n,was obtained under hydrothermal conditions of 1,3-di（pyridineyl）benzene（dpb） and 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）（H2hfipbb）. The title compound reveals a three-dimensional（3D） framework with two types of helical chains [Cd（COO）]n,which are linked each other to further form a double helical chain [Cd2（COO）2]n by sharing the same Cd（Ⅱ） ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.展开更多
A mixture of (S, S)-bis(oxazoline) ligand (1) with silver trifluoromethane sulfonate afforded a helical coordination polymer (2). Its structure was determined by X-ray angle-crystal diffraction.
文摘A coordination polymer [Co(dpa)prz0.5]n(1) with double-helix chains has been constructed hydrothermally using H2dpa(H2dpa=diphenic acid),prz(prz=piperazine) and Co(NO3)2.6H2O.The structure and magnetic properties of the complex were investigated.The complex crystallizes in triclinic system and P1 space group.Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry.Two carboxylates of the H2dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical-C-O-Co-chains.The two types of helical chains are interconnected to each other through the Co (Ⅱ) centers to produce double-helix chains.The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains.The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks.Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions.
基金the financial support by the Science and Technology Research Key Project Department of Education in Henan Province(14A150026)Nanyang Normal University Scientific Research Foundation Project(ZX2014041)
文摘A new 3D complex,[Co（L）（bpe）0.5（H2O）2]n（1,H2 L = 5-iodo-benzene-1,3-dioxyacetic acid,bpe = 1,2-bis（4-pyridyl）ethylene）,has been hydrothermally synthesized and structurally characterized by elemental analysis,IR and X-ray diffraction.It is formulated as C16H16 Co INO8,crystallizes in monoclinic,space group P21/c,with a = 9.806（2）,b = 6.5492（13）,c = 28.187（8） A,β = 100.12（3）°,V = 1782.0（7） A^3,Z = 4,Dc = 1.998 g/m^3,F（000） = 1052,Μr = 536.13,the final R = 0.0393 and w R = 0.0858 for 3134 observed reflections with I 〉 2σ（I）.Complex 1 displays a 3D framework with multiform helical features,left-and right-handed triple helical braids and single helical chains,which can be simplified as a new type of（3,4）-connected lattice with a（6·10^2）（6^2·10^4） SchlAfli symbol.Moreover,the thermal analysis of complex 1 has also been investigated.
文摘An air and moisture stable ruthenium（Ⅲ） formate complex[Ru（HCO2）Cl2]n has been synthesized and examined in the epoxidation of substituted styrenes.X-ray crystallographic data of this complex were determined and showed that the formate ligand coordinates to the ruthenium centers in a μ~2-η~2 fashion（syn,syn）.Its asymmetric unit contains one Ru（Ⅲ） ion together with the half of a formate ligand and one chloride anion,which are bridged between the metal centers,forming a 1-D chain coordination polymer.This electron deficient helical coordination polymer was employed in the epoxidation of parafluorostyrene,affording the epoxide product in 92%yield.Natural chirality of this coordination polymer is applicable in asymmetric epoxidation reactions.
基金financially supported by the National Natural Science Foundation of China (Nos. 21622402, 51673057 and 21574036)the 1000 plan Program for Young Talents of China
文摘Three novel enantiopure phenyl isocyanide monomers with BH3-protected phosphine functional group were designed and synthesized. Polymerization of these monomers using a alkyne-Pd（II） complex as a catalyst led to the formation of respective helical polyisocyanides in high yields with controlled molecular weights（Mns） and narrow molecular weight distributions（Mw/Mns）. Removing the protecting BH3 groups afforded helical poly（phenyl isocyanide）s bearing phosphine pendants. Thanks to the chiral induction of monomer, the isolated helical polyisocyanides showed high optical activity, as revealed by circular dichroism（CD） and absorption spectroscopies and polarimetry. The helical structures of these polymers were quite stable in various organic solvents with different polarities and in a wide temperature range. Moreover, these helical polymers could be used as organocatalysts and showed good performance in enantioselective cross Rauhut-Currier reaction. The enantiomeric excess（ee） values of the isolated products of cross Rauhut-Currier reaction could be up to 90%. The polymer organocatalysts could be easily recovered from the reaction mixtures and reused at least five times in the reaction without significant loss of their enantioselectivities and catalytic activities.
基金supported by Education Chamber of Henan Province(No.15A150068)
文摘Two novel coordination polymers with helical chains, {[Zn（L）（H2O）]·H2O}n（1） and {[Zn（L）（p-bix）]·3.5H2O}n（2）, where H2 L = 5-（4-hydroxypyridinium-1-ylmethyl） isophthalic acid and p-bix = 1,4-bis（imidazol-1-ylmethyl）benzene, have been hydrothermally synthesized, and charac-terized by elemental analysis, powder X-ray diffraction（PXRD）, IR, thermal gravimetric analyses（TGA） and also by single-crystal X-ray diffraction. Both complexes 1 and 2 crystallize inmonoclinic, space group P21/c. Compound 1 displays a two-dimensional（2D） structure with two distinct types of helical chains; 2 shows a layered coordination polymer with two types of helical chains and features an interesting 2D→3D interdigitated architecture. Meanwhile, the luminescent properties of 1 and 2 have also been investigated in detail.
文摘A novel manganese（Ⅱ） coordination polymer with 2-（4-carboxyphenoxy） benzoic acid （2,4＇-H2oba） and 1,10-phenanthroline （1,10-phen） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and elemental analysis. Compound [Mn（2,4＇-oba）（1,10-phen）] is of monoclinic system, space group P21/n with a = 7.960（1）, b = 15.464（2）, c = 18.703（3）A, β = 99.976（2）°, V = 2267.5（6） A^3, Z = 4, Mr = 491.35, Dc = 1.439 g/cm^3, F（000） = 1004 and μ = 0.623 cm·1. The final R = 0.0419 and wR = 0.0978 for 3444 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the oba2-ligands adopt a bis（chelating bidentate） mode to link two Mn（Ⅱ） centers to form an infinite 1D helical chain. Furthermore, a 3D supramolecular structure was formed by π-π stacking interactions and hydrogen bonds.
基金Supported by the National Natural Science Foundation of China（No.20701015）.
文摘Two novel 2D coordination polymers, [Co（BPDC）DMSO]·DMSO（1）（BPDC=2,2＇-bipyridyl-4,4＇-dicar- boxylic acid） and [Zn（BPDC）DMF]·DMF（2）, were synthesized from 2,2＇-bipyridyl-4,4＇-dicarboxylic acid ligand （H2BPDC） under solvothermal conditions. Single crystal X-ray diffraction analyses reveal that compound 1 crystal- lizes in orthorhombic system and Pca21 space group with a=1.29628（13） nm, b=1.13721（13） nm, c=1.66457（19） nm, α=90°, β=90°, γ=90°, V=2.4538（5） nm3. Compound 2 crystallizes in monoclinic system and P21/c space group with a=0.9429（6） nm, b=1.4757（10） nm, c=1.5980（9） nm, α=90°, β=114°, γ=90°, V=2.030（2） nm3. Compounds 1 and 2 exhibit two different 3-connected hcb and fes topologies, respectively. The structures of the two compounds both contain interesting characters of double-helical chains（left- and right-handed helical chains）. Additionally, the mag- netic and luminescent properties of the two compounds were studied.
基金Supported by the National Natural Science Foundation of China(No.21373132)the Science Foundation of Shaanxi University of Technology(No.SLGKY-36)
文摘A new AgO） coordination polymer, {[Ag（1,3-BIP）（H20）][Ag（1,3- BIP）（PMA）0.5.- 4H20}n （PMA = 1,2,4,5-benzenetricarboxylic acid, 1,3-BIP = 1,3-bis（imidazole）propane）, have been synthesized and characterized by single-crystal X-ray diffraction, powder XRD, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that the title complex is formed by 1D polymeric cationic chains of [Ag（1,3-BIP）（H2O）]n^n＋ and 2D polymetric anionic layer of [Ag（1,3-BIP）（PMA）0.5]n^n-, which are further linked by intermolecular H-bonding to form a 3D supramolecular framework. In addition, the photoluminescence property of the title complex in the solid state at room temperature was also investigated.
基金supported by the Natural Science Foundation of Guizhou Province(20122344)125 program of Guizhou Education Department(2012015)the Doctoral Scientific Fund of Zunyi Normal College(2012BSJJ12)
文摘5-（Hydroxymethyl） isophthalic acid （H2HIA） as a novel organic ligand was prepared from 3,5-bis（methoxycarbonyl）benzoic acid by a two-step method. And then, a 3D helical coor- dination polymer with a 3-fold interpenetration structure, namely [Zn1/2（HIA）1/2（DPEE）1/2]n （1）, was hydrothermally synthesized at 160 ℃, using H2HIA ligands to assemble with DPEE ligands and Zn2＋ ions. Complex 1 crystalizes in orthorhombic system, space group Pnna, with a = 8.2118（5）, b = 17.1698（7）, c =14.9922（7） ？, V = 2113.82（18） ？3, μ = 1.194 mm-1, Z = 4 and S = 0.967. Moreover, some physical characteristics of complex 1, such as powder X-ray diffraction （PXRD）, thermogravimetry analyses （TGA） and photoluminescent properties, were also investigated.
基金supported by the National Natural Science Foundation of China(No.51477002,21301005)Natural Science Foundation of Anhui Province(1408085QB31)
文摘One new chiral metal-organic coordination polymer,[Cd2（dpb）（H2hfipbb）2]n,was obtained under hydrothermal conditions of 1,3-di（pyridineyl）benzene（dpb） and 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）（H2hfipbb）. The title compound reveals a three-dimensional（3D） framework with two types of helical chains [Cd（COO）]n,which are linked each other to further form a double helical chain [Cd2（COO）2]n by sharing the same Cd（Ⅱ） ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.
基金Project supported by the National Natural Science Foundation of China (NO. 29525202), Chinese Academy of Sciences, and Shanghai Municipal Committee of Science and Technology (No. 98QA14001).
文摘A mixture of (S, S)-bis(oxazoline) ligand (1) with silver trifluoromethane sulfonate afforded a helical coordination polymer (2). Its structure was determined by X-ray angle-crystal diffraction.
