New heteroleptic and homoleptic complexes of the type[Pd（4,5-dmbipy）C12], [Pd（4,5-dmbipy）L2], and [Pd（4,5-dimebipy）2]2＋ （L = Pyridine or 4-methylpyridine（4-picoline）, bipy = 2,2＇-bipyridine, and 4,5-dimebip...New heteroleptic and homoleptic complexes of the type[Pd（4,5-dmbipy）C12], [Pd（4,5-dmbipy）L2], and [Pd（4,5-dimebipy）2]2＋ （L = Pyridine or 4-methylpyridine（4-picoline）, bipy = 2,2＇-bipyridine, and 4,5-dimebipy = 4,5-dimethyl-2,2＇-bipyridine） were synthesized and characterized by IH NMR and elemental analysis. The crystal structure of bis（4-methylpyridine）-4,5- dimethyl-2,2＇-bipyridinepalladium（II）perchlorate [Pd（4,5-dmbipy）（4-pic）2]（CIO4）2 was also determined by single crystal X-ray diffraction. This complex crystallized in the triclinic crystal system and space group PI with a = 9.562 （2）, b = 11.326 （4）, c = 15.0120 （10） A°; α = 70.940°, β= 77.60 （2）, γ= 67.86 （2） and z = 4. The Pd （II） in square planar environment showed a small distortion towards tetrahedral through one coordinated bipyridine ring twisting with respect to the other.展开更多
Two new Cu（II） coordination polymers, [Cu（FDA）（BPY）（H20）]n （1） and {[Cu（FDA）（BPY）（H2O）].2H2O}n （2） （H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2＇-bipyridine）, have been synthesized and structural...Two new Cu（II） coordination polymers, [Cu（FDA）（BPY）（H20）]n （1） and {[Cu（FDA）（BPY）（H2O）].2H2O}n （2） （H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2＇-bipyridine）, have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 7.5915（15）, b = 8.4050（17）, c = 24.204（6） A, β = 99.05（3）°, V= 1525.1（6） A3, Dc = 1.706 g/crn3, C16HI2CuN206, Mr = 391.82, F（000） = 796, μ（MoKa） = 1.470 mm-l, Z = 4, R = 0.0633 and wR = 0.1059 for 2389 observed reflections （1 〉 2a（I））, R = 0.0738, and wR = 0.1098 for all data. Complex 2 belongs to triclinic space group PI with a = 8.8660（18）, b = 8.9112（18）, c = 12.525（3） A, a = 88.41（3）, β = 69.38（3）, γ = 66.95（3）°, V = 845.2（3） A3, Dc = 1.681 g/cm3, CI6HI6CuN2Os, Mr. = 427.85, F（000） = 438, μ（MoKα） = 1.342 mm-1, Z = 2, R = 0.0290 and wR = 0.0690 for 2767 observed reflections （I 〉 2σ（I））, R = 0.0329 and wR = 0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.展开更多
A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffrac...A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a = 7.4782（14）, b = 10.1400（11）, c = 16.6982（14） , α = 103.494（11）, β = 91.996（13）, γ = 103.829（12）o, C26H32Cl2N2Rh2, Mr = 649.26, V = 1190.0（3）3, Dc = 1.812 g/cm3, Z = 2, F（000） = 652, μ（Mo Kα） = 1.629 mm-1, R = 0.0286 and w R = 0.0463 for 3718 observed reflections（I 2σ（I））. The complex was linked to form 1D chains by hydrogen bonding interaction（C–H···Cl）, and further to construct a 2D layer structure by π···π stacking interactions between the pyridine rings of 2,2＇-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.展开更多
Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic ...Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.展开更多
The title complex Pd（H2BDA）Cl2·2DMSO （C16H14Cl2N2O6PdS2, H2BDA = 2,2＇- bipyridine-3,3＇-dicarboxylic acid） has been synthesized and characterized by IR spectra, elemental analysis and ^1H NMR spectra. Its st...The title complex Pd（H2BDA）Cl2·2DMSO （C16H14Cl2N2O6PdS2, H2BDA = 2,2＇- bipyridine-3,3＇-dicarboxylic acid） has been synthesized and characterized by IR spectra, elemental analysis and ^1H NMR spectra. Its structure was determined by single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P2（1/c） with a = 1.3604（6）, b = 1.2606（6）, c = 1.3521 （6） nm, β = 103.677（7）°, V = 2.2530（17） nm^3, Mr = 571.75, Z = 4, Dc = 1.686 g/cm^3,μ = 1.280 mm^-1, F（000） = 1136, R= 0.0405 and wR= 0.0908. The complex presents a planar quadrangle arrangement and is assembled via hydrogen bonds.展开更多
There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this produ...There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this product via the oxidation of 4,4′ bismethyl 2,2′ bipyridine, followed by esterification and reduction. The yield increases and the reaction conditions become genial in contrast to those of other methods. The molecular structure of the final product was confirmed by means of elemental analysis, IR, 1H NMR and MS spectra.展开更多
A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） an...A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.展开更多
Bimetallic Pd-Cu/Al_(2)O_(3) was prepared by wetness impregnation method and its catalytic activity on coupling reaction of pyridine to 2,2'-bipyridine was assessed in view of the effects of different molar ratios...Bimetallic Pd-Cu/Al_(2)O_(3) was prepared by wetness impregnation method and its catalytic activity on coupling reaction of pyridine to 2,2'-bipyridine was assessed in view of the effects of different molar ratios of Pd:Cu.It is found that Pd-Cu/Al_(2)O_(3) has the small particle size and good dispersion through the characterization.Compared with Pd/Al_(2)O_(3),Pd-Cu(1:2)/Al_(2)O_(3) is the preferable catalyst under the optimum conditions of 1 MPa N2 pressure,310℃and 16 h.The conversion of pyridine is 35.4%,and the selectivity for 2,2'-Bipyridine is up to 99%,which is much higher activity than Pd/Al_(2)O_(3).The directly coupled synthesis meets the requirements of the atomic economy better.The addition of Cu also reduces the dosage of Pd and lowers the cost.It is worth noting that the recycled Pd-Cu/Al_(2)O_(3) catalyst still shows high activity and stability after three times.展开更多
Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare ear...Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare earth chloride RECl_3 , respectively, in alcohol solution. The compositions were characterized by means of infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. Luminescent properties of the three complexes were studied. At room temperature, under UV light excitation, the Sm^(3+) , Eu^(3+) , and Tb^(3+) complexes exhibit characteristic emission of the central ions. The fluorescence spectra show that the fluorescence emission intensity of Eu^(3+) complex is the strongest. The narrow strongest emission band of Eu^(3+) complex is considered to be a valuable material with bright red fluorescence.展开更多
文摘New heteroleptic and homoleptic complexes of the type[Pd（4,5-dmbipy）C12], [Pd（4,5-dmbipy）L2], and [Pd（4,5-dimebipy）2]2＋ （L = Pyridine or 4-methylpyridine（4-picoline）, bipy = 2,2＇-bipyridine, and 4,5-dimebipy = 4,5-dimethyl-2,2＇-bipyridine） were synthesized and characterized by IH NMR and elemental analysis. The crystal structure of bis（4-methylpyridine）-4,5- dimethyl-2,2＇-bipyridinepalladium（II）perchlorate [Pd（4,5-dmbipy）（4-pic）2]（CIO4）2 was also determined by single crystal X-ray diffraction. This complex crystallized in the triclinic crystal system and space group PI with a = 9.562 （2）, b = 11.326 （4）, c = 15.0120 （10） A°; α = 70.940°, β= 77.60 （2）, γ= 67.86 （2） and z = 4. The Pd （II） in square planar environment showed a small distortion towards tetrahedral through one coordinated bipyridine ring twisting with respect to the other.
基金Supported by the National Natural Science Foundation of China(21031002 and 51073079)the Fundamental Research Funds for the Central Universitiesthe Application and Research in Cutting-edge Technologies in Tianjin Technology Projects in General(K11JCYBJC11100)
文摘Two new Cu（II） coordination polymers, [Cu（FDA）（BPY）（H20）]n （1） and {[Cu（FDA）（BPY）（H2O）].2H2O}n （2） （H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2＇-bipyridine）, have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 7.5915（15）, b = 8.4050（17）, c = 24.204（6） A, β = 99.05（3）°, V= 1525.1（6） A3, Dc = 1.706 g/crn3, C16HI2CuN206, Mr = 391.82, F（000） = 796, μ（MoKa） = 1.470 mm-l, Z = 4, R = 0.0633 and wR = 0.1059 for 2389 observed reflections （1 〉 2a（I））, R = 0.0738, and wR = 0.1098 for all data. Complex 2 belongs to triclinic space group PI with a = 8.8660（18）, b = 8.9112（18）, c = 12.525（3） A, a = 88.41（3）, β = 69.38（3）, γ = 66.95（3）°, V = 845.2（3） A3, Dc = 1.681 g/cm3, CI6HI6CuN2Os, Mr. = 427.85, F（000） = 438, μ（MoKα） = 1.342 mm-1, Z = 2, R = 0.0290 and wR = 0.0690 for 2767 observed reflections （I 〉 2σ（I））, R = 0.0329 and wR = 0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.
基金Supported by the National Natural Science Foundation of China(Nos.2126102021361022)+2 种基金the Scientific and Technological Landing Project of Higher Education of Jiangxi Province(No.KJLD12094)the College Students’ Innovative Education Program of Jiangxi Provincethe Leading Talent Training Plan of "Xinjiang 866 Engineering Excellence"of Shangrao city
文摘A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a = 7.4782（14）, b = 10.1400（11）, c = 16.6982（14） , α = 103.494（11）, β = 91.996（13）, γ = 103.829（12）o, C26H32Cl2N2Rh2, Mr = 649.26, V = 1190.0（3）3, Dc = 1.812 g/cm3, Z = 2, F（000） = 652, μ（Mo Kα） = 1.629 mm-1, R = 0.0286 and w R = 0.0463 for 3718 observed reflections（I 2σ（I））. The complex was linked to form 1D chains by hydrogen bonding interaction（C–H···Cl）, and further to construct a 2D layer structure by π···π stacking interactions between the pyridine rings of 2,2＇-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.
基金supported by the National Natural Science Foundation of China (No.20872057)
文摘Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.
基金This project was supported by the Science Foundation of Shenyang Institute of Chemical Technology, National Science Foundation for Post-doctoral and Corporation Post-doctoral Foundation of Liaoning Province
文摘The title complex Pd（H2BDA）Cl2·2DMSO （C16H14Cl2N2O6PdS2, H2BDA = 2,2＇- bipyridine-3,3＇-dicarboxylic acid） has been synthesized and characterized by IR spectra, elemental analysis and ^1H NMR spectra. Its structure was determined by single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P2（1/c） with a = 1.3604（6）, b = 1.2606（6）, c = 1.3521 （6） nm, β = 103.677（7）°, V = 2.2530（17） nm^3, Mr = 571.75, Z = 4, Dc = 1.686 g/cm^3,μ = 1.280 mm^-1, F（000） = 1136, R= 0.0405 and wR= 0.0908. The complex presents a planar quadrangle arrangement and is assembled via hydrogen bonds.
基金Supported by the National Natural Science Foundation of China(No. 2 0 16 2 0 0 5 ) the Foundation of EducationMinistry(No. 2 0 0 1- 3) .
文摘There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this product via the oxidation of 4,4′ bismethyl 2,2′ bipyridine, followed by esterification and reduction. The yield increases and the reaction conditions become genial in contrast to those of other methods. The molecular structure of the final product was confirmed by means of elemental analysis, IR, 1H NMR and MS spectra.
基金Supported by the Natural Science Foundation of Zhejiang Province (Y407301)
文摘A novel crystal with the molecular formula [Pd（DCA）（bipy）]2 [Pd（bipy）Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate （Na2 （DCA）,DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate） and 2,2-bipyidine （bipy） through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818（7）,b=14.8426（8）,c=15.0043（8）,α=97.319（3）,β=92.521（3）,γ=105.776（2）°,V=2898.4（3） 3,Dc=1.545 g·cm-3,Z=1,F（000）=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections （I〉2σ（I））.The binding reaction of the complex with ct-DNA and bovine serum albumin （BSA） was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells （SMMC7721） in vitro is much higher than that of Na 2 （DCA）.
基金by the Natural Science Foundation of the Higher Education Institutions of Anhui Province(No.KJ2021A0132)the Key Research and Development Program of Anhui Province(No.202104a05020070)the National and Anhui Province College Student Innovation Training Program(Nos.202110364055 and S202010364145)。
文摘Bimetallic Pd-Cu/Al_(2)O_(3) was prepared by wetness impregnation method and its catalytic activity on coupling reaction of pyridine to 2,2'-bipyridine was assessed in view of the effects of different molar ratios of Pd:Cu.It is found that Pd-Cu/Al_(2)O_(3) has the small particle size and good dispersion through the characterization.Compared with Pd/Al_(2)O_(3),Pd-Cu(1:2)/Al_(2)O_(3) is the preferable catalyst under the optimum conditions of 1 MPa N2 pressure,310℃and 16 h.The conversion of pyridine is 35.4%,and the selectivity for 2,2'-Bipyridine is up to 99%,which is much higher activity than Pd/Al_(2)O_(3).The directly coupled synthesis meets the requirements of the atomic economy better.The addition of Cu also reduces the dosage of Pd and lowers the cost.It is worth noting that the recycled Pd-Cu/Al_(2)O_(3) catalyst still shows high activity and stability after three times.
基金supported by the National Natural Science Foundation of China(No.21141008)the Natural Science Foundation of Inner Mongolia,China(No.2009MS0205)Baotou Science and Technology Bureau,China(No.2010J2004)
文摘Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare earth chloride RECl_3 , respectively, in alcohol solution. The compositions were characterized by means of infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. Luminescent properties of the three complexes were studied. At room temperature, under UV light excitation, the Sm^(3+) , Eu^(3+) , and Tb^(3+) complexes exhibit characteristic emission of the central ions. The fluorescence spectra show that the fluorescence emission intensity of Eu^(3+) complex is the strongest. The narrow strongest emission band of Eu^(3+) complex is considered to be a valuable material with bright red fluorescence.
