A dinuclear complex [DyFe(CN)6(DMF)4(H2O)3]·1.25H2O (DMF=N, N dimethylformamide) 1 based on the cyanide as linkage was prepared and structurally characterized by X ray single crystal structure analysis. The Dy?io...A dinuclear complex [DyFe(CN)6(DMF)4(H2O)3]·1.25H2O (DMF=N, N dimethylformamide) 1 based on the cyanide as linkage was prepared and structurally characterized by X ray single crystal structure analysis. The Dy?ion is eight coordinations in a square antiprism arrangement and the Fe?ion is six coordinations oriented octahedrally. The neutral units [DyFe(CN)6(DMF)4(H2O)3] are held together by hydrogen bonds formed by lattice water molecules, coordinated water molecules and nitrogen atoms of cyanide coming from other distinct complex units to afford a three dimensional framework. CCDC: 192314.展开更多
以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH...以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH2Cl2(2)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2v、D2d和C2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K (1)、40.5 K (2)、53.8和13.4 K (3),且配合物1和3有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy-O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。展开更多
A new complex of Ce2L·6H2O(here L=2,6-bis[bis(carboxylatomethyl)amino]methylg-4-chlorophenolate and abbreviated as Cl-HXTA) was synthezied and characterized by IR and EA.Kinetic study on the hydrolysis of the pho...A new complex of Ce2L·6H2O(here L=2,6-bis[bis(carboxylatomethyl)amino]methylg-4-chlorophenolate and abbreviated as Cl-HXTA) was synthezied and characterized by IR and EA.Kinetic study on the hydrolysis of the phosphordiester model compound,BDNPP promoted by the Ce2(III)-L complex was investigated by UV-Vis methods at 25,37℃,and pH 7.20.The result showed that the Ce(Ⅲ) complex could hydrolyze the phosphordiester effectively,with the rate constants as k=626.7 and 821.3(mol/L)-1 min-1,and half lives as 127.65 and 97.41min,reapectively under 25 and 37℃.The investigation on the interaction between the complex and CT DNA indicated that the absorbance of CT DNA was increased and the maximum peak(λmax=260 nm) blue-shifted,while the intensity of fluorescence spectra of EB-DNA was gradually weakened.展开更多
As a monoatomic bridge,fluoride ion can transmit efficient magnetic interaction between lanthanide ions but its effect on tuning the magnetization dynamics has not been well understood.Herein,two monofluoride-bridged ...As a monoatomic bridge,fluoride ion can transmit efficient magnetic interaction between lanthanide ions but its effect on tuning the magnetization dynamics has not been well understood.Herein,two monofluoride-bridged dinuclear dysprosium complexes[Dy_(2)F(bbpen)_(2)(Et OH)_(2)]Br·Et OH(1)and[Dy_(2)F(bbppy)_(2)]Br·2Et OH(2)with Dy-F-Dy angles of~178°and their diamagnetic-ion diluted analogues 1'and 2'were synthesized.Magnetic studies reveal that 1 and 1'barely show any magnetization dynamics,but 2 and 2'exhibit strong magnetization dynamics.Systematical experimental analysis combined with ab initio calculations reveals that the different magnetization dynamics between 1 and 2 mainly originate from the effect of magnetic anisotropy by terminal ligand and bridging group of the chelating ligand,and the fluoride bridge can effectively suppress the quantum tunneling of the magnetization and turn on Orbach process in 2.展开更多
Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we de...Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.展开更多
Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHT...Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [Gd2( IPHTA) (Mez-phen)4 (ClO4)2] (ClO4)2 complex were measured in the temperature range of 4-300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2, giving the exchange parameter J =- 0.19 cm-1 . This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(Ⅲ)-Gd(Ⅲ) ions within the complex.展开更多
文摘A dinuclear complex [DyFe(CN)6(DMF)4(H2O)3]·1.25H2O (DMF=N, N dimethylformamide) 1 based on the cyanide as linkage was prepared and structurally characterized by X ray single crystal structure analysis. The Dy?ion is eight coordinations in a square antiprism arrangement and the Fe?ion is six coordinations oriented octahedrally. The neutral units [DyFe(CN)6(DMF)4(H2O)3] are held together by hydrogen bonds formed by lattice water molecules, coordinated water molecules and nitrogen atoms of cyanide coming from other distinct complex units to afford a three dimensional framework. CCDC: 192314.
文摘以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH2Cl2(2)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2v、D2d和C2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K (1)、40.5 K (2)、53.8和13.4 K (3),且配合物1和3有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy-O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。
基金Supported by the National Natural Science Foundation of China(21601132 21471051)+2 种基金the Education Department of Heilongjiang Province Basic Scientific Research Operating Costs Research Project(KYYWF10236180110)the Doctoral Scientific Research Foundation of Suihua University(SQ18002)the Fourth Scientific Research and Innovation Team(SIT04B004)
文摘A new complex of Ce2L·6H2O(here L=2,6-bis[bis(carboxylatomethyl)amino]methylg-4-chlorophenolate and abbreviated as Cl-HXTA) was synthezied and characterized by IR and EA.Kinetic study on the hydrolysis of the phosphordiester model compound,BDNPP promoted by the Ce2(III)-L complex was investigated by UV-Vis methods at 25,37℃,and pH 7.20.The result showed that the Ce(Ⅲ) complex could hydrolyze the phosphordiester effectively,with the rate constants as k=626.7 and 821.3(mol/L)-1 min-1,and half lives as 127.65 and 97.41min,reapectively under 25 and 37℃.The investigation on the interaction between the complex and CT DNA indicated that the absorbance of CT DNA was increased and the maximum peak(λmax=260 nm) blue-shifted,while the intensity of fluorescence spectra of EB-DNA was gradually weakened.
基金supported by the National Key R&D Program of China(No.2018YFA0306002)the National Natural Science Foundation of China(Nos.21971123 and 21973046)the Natural Science Foundation of Tianjin(No.18JCJQJC47200)。
文摘As a monoatomic bridge,fluoride ion can transmit efficient magnetic interaction between lanthanide ions but its effect on tuning the magnetization dynamics has not been well understood.Herein,two monofluoride-bridged dinuclear dysprosium complexes[Dy_(2)F(bbpen)_(2)(Et OH)_(2)]Br·Et OH(1)and[Dy_(2)F(bbppy)_(2)]Br·2Et OH(2)with Dy-F-Dy angles of~178°and their diamagnetic-ion diluted analogues 1'and 2'were synthesized.Magnetic studies reveal that 1 and 1'barely show any magnetization dynamics,but 2 and 2'exhibit strong magnetization dynamics.Systematical experimental analysis combined with ab initio calculations reveals that the different magnetization dynamics between 1 and 2 mainly originate from the effect of magnetic anisotropy by terminal ligand and bridging group of the chelating ligand,and the fluoride bridge can effectively suppress the quantum tunneling of the magnetization and turn on Orbach process in 2.
基金financially supported by the National Key R&D Program of China (No. 2021YFA1501700)the National Natural Science Foundation of China+1 种基金Basic Science Center Program (No.51988102)the National Natural Science Foundation of China (No. 52073272)
文摘Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.
基金Project supported by the Natural Science Foundation of Shandong Province (No. Y97-D17076) the National Natural Science Foundation of China (No. 29631040)
文摘Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [Gd2( IPHTA) (Mez-phen)4 (ClO4)2] (ClO4)2 complex were measured in the temperature range of 4-300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2, giving the exchange parameter J =- 0.19 cm-1 . This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(Ⅲ)-Gd(Ⅲ) ions within the complex.
