A new binuclear cobalt(Ⅱ)complex,[Co2(C10H6NO2)2(C12H8N2)2(N3)2]·H2O(1,C10H6NO2-:isoquinoline-1-carboxylate,C12H8N2:1,10-phenanthroline(phen);N3-:azide),has been synthesized though a mixed-solvothermal method us...A new binuclear cobalt(Ⅱ)complex,[Co2(C10H6NO2)2(C12H8N2)2(N3)2]·H2O(1,C10H6NO2-:isoquinoline-1-carboxylate,C12H8N2:1,10-phenanthroline(phen);N3-:azide),has been synthesized though a mixed-solvothermal method using the pentanol and distilled water as solvent.The complex was characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction.It crystallizes in triclinic system,space group P1 with Z=2,a=1.777(5),b=11.815(5),c=17.141(7)?,α=74.496(6)°,β=70.537(6)°,γ=67.861(6)°,V=2055.4(14)?3,Mr=922.66,Dc=1.491 g/cm3,λ=0.71073?,μ=0.870 mm-1,F(000)=942,R=0.0455 and wR=0.1147 for 4960 observed reflections with I>2σ(I)and S=1.129.Its molecular structure is constructed by two Co2+cations,two chelating phen ligands,two chelating isoquinoline-1-carboxylate ligands,two bridging linear azide anions and two uncoordinated half-occupied water molecules.The 3-D supramolecular network results from the multiple hydrogen bonds andπ-πstacking interactions among three types of ligands.More importantly,its thermal stability,luminescent properties and magnetic properties have also been studied in detail.展开更多
Three new binuclear cobalt (II) complexes with extended tetracarboxylato-bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA)(NO2phen)4 (3), where PMTA...Three new binuclear cobalt (II) complexes with extended tetracarboxylato-bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA)(NO2phen)4 (3), where PMTA represents the tetraanion of pyromellitic acid, and bpy, phen, NO2-phen denote 2,2-bipyridine, 1,10-phenanthroline; 5-nitro-1, 10-phenanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt(II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4–300 K) and the observed data were successfully simulated by th e equation based on the spin Hamiltonian operator, ?=?2J ?1·?2, giving the exchange integral J= ?1.02 cm?1 for 1, J= ?1.21 cm?1 for 2 and J = ?1.18 cm?1 for 3, respectively. These results revealed the operation of antiferromagnetic spin-exchange interaction between the two Co(II) ions within each molecule.展开更多
A novel binuclear cobalt complex with mixed valence state Co(Ⅰ)Co(Ⅱ)(μ-Ph_2Ppy)_2(μ-CO)_2Cl_3 has been prepared, Ph_2Ppy=2-(diphenyl phosphino)pyridine, and its molecular structure determined by using 3569 indepen...A novel binuclear cobalt complex with mixed valence state Co(Ⅰ)Co(Ⅱ)(μ-Ph_2Ppy)_2(μ-CO)_2Cl_3 has been prepared, Ph_2Ppy=2-(diphenyl phosphino)pyridine, and its molecular structure determined by using 3569 independent reflections. The complex was crystallized in the orthorhomblc space group P2_1nb with a=13.32(1), b=14.31(1),c=18.94(2) and Z=4. The structure was solved by direct method and full-matrix least squares refinement carried out. The final R value is 0.072.If the Co-Co bond is not taken into account, two cobalt atoms exhibit a five-coordlnate reformed trigonal bipyramid configuration (formal oxidation state +1) and a six-coordinate reformed octahedral configuration (formal oxidation state +2), respectively. The Co-Co distance is 2.685(1). The molecule belongs to the C_(2v), point group. A new W-frame compound with mixed valence state Co(0)Co(Ⅰ)(μ-Ph_2Ppy)_2(μ-CO)(CO)Cl can be formed by reducing this complex.展开更多
A direct method of obtaining complexes of cobalt with respect to rare earth elements is reported. The total of 14 new compounds which are insoluble in water and general organic media have been synthesized by the react...A direct method of obtaining complexes of cobalt with respect to rare earth elements is reported. The total of 14 new compounds which are insoluble in water and general organic media have been synthesized by the reaction of RE（Ac）<sub>3</sub>·XH<sub>2</sub>O （RE=rare earth elements except for Ce, Pm; X=2, 5, 8） with [H<sub>6</sub>CO<sub>2</sub>（Gc）<sub>5</sub>CS<sub>2</sub>] （Gc=<sup>-</sup>S<sub>2</sub>CNHCH<sub>2</sub>CO<sub>2</sub><sup>-</sup>） in acetone/ water at room temperature. The complexes having the general formula, [RE<sub>2</sub>Co<sub>2</sub>（Gc）<sub>5</sub>HAcCS<sub>2</sub>·XH<sub>2</sub>O], were characterized by elemental analyses, infrared spectra, DSC and TGA.展开更多
A new highly selective thiocyanate PVC membrane electrode based on bisbebzoin-semitriethylenetetraamine binuclear cobalt(Ⅱ) metallic complex [Co(Ⅱ) 2-BBSTA] as neutral carrier is reported, which displays an anti-Hof...A new highly selective thiocyanate PVC membrane electrode based on bisbebzoin-semitriethylenetetraamine binuclear cobalt(Ⅱ) metallic complex [Co(Ⅱ) 2-BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0×10 -1 to 1.0×10 -6 mol/L with a detection limit 8.0×10 -7 mol/L and a slope of -52.0 mV/dec in phosphorate buffer solution of pH=5.0 at 25 ℃. The response mechanism is discussed in view of the a.c. impedance technique and the UV spectroscopy technique. The electrode based on binuclear cobalt(Ⅱ) compound was used to determine the thiocyanate content in waste water with satisfactory results.展开更多
The complexCo 2 Cl 2 (EGTB)·(ClO 4 ) 2 ·5H 2 O was synthesized in methanol-aqueous solution and its crystal structure was determined by X-ray di ffraction method.The crystal belon gs to monoclinic with space...The complexCo 2 Cl 2 (EGTB)·(ClO 4 ) 2 ·5H 2 O was synthesized in methanol-aqueous solution and its crystal structure was determined by X-ray di ffraction method.The crystal belon gs to monoclinic with space group of P2 1 /c.The cell parameters are a=1.42231(2)nm,b=2.53181(3)nm,c=1.43392(2)nm,β=102.0518(5)°,Z =4,F(000)=2360,D c =1.508g·cm -3 ,The final R=0.0788,w R 2 =0.232,The catalytic rate constant of the dismutation of superoxide radic als has been obtained by means of photo reduction of nitroblue tetrazoliu m(NBT),and it is 1.875×10 6 mol -1 ·L·s -1 .展开更多
采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催...采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催化性能,在室温下、双核酞菁钴用量为0.01 g(cat)/5 m L、空气流量为80 m L/min、反应温度为40℃、反应1 h,DBT脱硫率达到97.17%。催化剂重复使用5次,催化效果无明显下降。氧化产物经红外光谱、质谱分析为DBTO2。对芳香烃及烯烃进行了催化氧化实验,发现该工艺对油品的质量基本无影响。展开更多
基金Project supported by the National Natural Science Foundation of China (No. 21601095)。
文摘A new binuclear cobalt(Ⅱ)complex,[Co2(C10H6NO2)2(C12H8N2)2(N3)2]·H2O(1,C10H6NO2-:isoquinoline-1-carboxylate,C12H8N2:1,10-phenanthroline(phen);N3-:azide),has been synthesized though a mixed-solvothermal method using the pentanol and distilled water as solvent.The complex was characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction.It crystallizes in triclinic system,space group P1 with Z=2,a=1.777(5),b=11.815(5),c=17.141(7)?,α=74.496(6)°,β=70.537(6)°,γ=67.861(6)°,V=2055.4(14)?3,Mr=922.66,Dc=1.491 g/cm3,λ=0.71073?,μ=0.870 mm-1,F(000)=942,R=0.0455 and wR=0.1147 for 4960 observed reflections with I>2σ(I)and S=1.129.Its molecular structure is constructed by two Co2+cations,two chelating phen ligands,two chelating isoquinoline-1-carboxylate ligands,two bridging linear azide anions and two uncoordinated half-occupied water molecules.The 3-D supramolecular network results from the multiple hydrogen bonds andπ-πstacking interactions among three types of ligands.More importantly,its thermal stability,luminescent properties and magnetic properties have also been studied in detail.
基金Project supported by the Natural Science Foundation of Shandong Province(No. Q99B12) and the National Natural Science Foundation of China (No. 29873031).
文摘Three new binuclear cobalt (II) complexes with extended tetracarboxylato-bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA)(NO2phen)4 (3), where PMTA represents the tetraanion of pyromellitic acid, and bpy, phen, NO2-phen denote 2,2-bipyridine, 1,10-phenanthroline; 5-nitro-1, 10-phenanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt(II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4–300 K) and the observed data were successfully simulated by th e equation based on the spin Hamiltonian operator, ?=?2J ?1·?2, giving the exchange integral J= ?1.02 cm?1 for 1, J= ?1.21 cm?1 for 2 and J = ?1.18 cm?1 for 3, respectively. These results revealed the operation of antiferromagnetic spin-exchange interaction between the two Co(II) ions within each molecule.
文摘A novel binuclear cobalt complex with mixed valence state Co(Ⅰ)Co(Ⅱ)(μ-Ph_2Ppy)_2(μ-CO)_2Cl_3 has been prepared, Ph_2Ppy=2-(diphenyl phosphino)pyridine, and its molecular structure determined by using 3569 independent reflections. The complex was crystallized in the orthorhomblc space group P2_1nb with a=13.32(1), b=14.31(1),c=18.94(2) and Z=4. The structure was solved by direct method and full-matrix least squares refinement carried out. The final R value is 0.072.If the Co-Co bond is not taken into account, two cobalt atoms exhibit a five-coordlnate reformed trigonal bipyramid configuration (formal oxidation state +1) and a six-coordinate reformed octahedral configuration (formal oxidation state +2), respectively. The Co-Co distance is 2.685(1). The molecule belongs to the C_(2v), point group. A new W-frame compound with mixed valence state Co(0)Co(Ⅰ)(μ-Ph_2Ppy)_2(μ-CO)(CO)Cl can be formed by reducing this complex.
文摘A direct method of obtaining complexes of cobalt with respect to rare earth elements is reported. The total of 14 new compounds which are insoluble in water and general organic media have been synthesized by the reaction of RE（Ac）<sub>3</sub>·XH<sub>2</sub>O （RE=rare earth elements except for Ce, Pm; X=2, 5, 8） with [H<sub>6</sub>CO<sub>2</sub>（Gc）<sub>5</sub>CS<sub>2</sub>] （Gc=<sup>-</sup>S<sub>2</sub>CNHCH<sub>2</sub>CO<sub>2</sub><sup>-</sup>） in acetone/ water at room temperature. The complexes having the general formula, [RE<sub>2</sub>Co<sub>2</sub>（Gc）<sub>5</sub>HAcCS<sub>2</sub>·XH<sub>2</sub>O], were characterized by elemental analyses, infrared spectra, DSC and TGA.
文摘A new highly selective thiocyanate PVC membrane electrode based on bisbebzoin-semitriethylenetetraamine binuclear cobalt(Ⅱ) metallic complex [Co(Ⅱ) 2-BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0×10 -1 to 1.0×10 -6 mol/L with a detection limit 8.0×10 -7 mol/L and a slope of -52.0 mV/dec in phosphorate buffer solution of pH=5.0 at 25 ℃. The response mechanism is discussed in view of the a.c. impedance technique and the UV spectroscopy technique. The electrode based on binuclear cobalt(Ⅱ) compound was used to determine the thiocyanate content in waste water with satisfactory results.
文摘The complexCo 2 Cl 2 (EGTB)·(ClO 4 ) 2 ·5H 2 O was synthesized in methanol-aqueous solution and its crystal structure was determined by X-ray di ffraction method.The crystal belon gs to monoclinic with space group of P2 1 /c.The cell parameters are a=1.42231(2)nm,b=2.53181(3)nm,c=1.43392(2)nm,β=102.0518(5)°,Z =4,F(000)=2360,D c =1.508g·cm -3 ,The final R=0.0788,w R 2 =0.232,The catalytic rate constant of the dismutation of superoxide radic als has been obtained by means of photo reduction of nitroblue tetrazoliu m(NBT),and it is 1.875×10 6 mol -1 ·L·s -1 .
文摘采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催化性能,在室温下、双核酞菁钴用量为0.01 g(cat)/5 m L、空气流量为80 m L/min、反应温度为40℃、反应1 h,DBT脱硫率达到97.17%。催化剂重复使用5次,催化效果无明显下降。氧化产物经红外光谱、质谱分析为DBTO2。对芳香烃及烯烃进行了催化氧化实验,发现该工艺对油品的质量基本无影响。
