Two heterometallic uranium oxyfluorides with hybrid networks were hydrothermally synthesized by incorporating two imidazoles, 1-（biphenyl-4-yl）-lH-imidazole （bpi） and 1,4-di（1H-imidazol-l-yl）ben- zene （dib）, f...Two heterometallic uranium oxyfluorides with hybrid networks were hydrothermally synthesized by incorporating two imidazoles, 1-（biphenyl-4-yl）-lH-imidazole （bpi） and 1,4-di（1H-imidazol-l-yl）ben- zene （dib）, formulated as Zn（bpi）2（UO2）2（H2O）F6 （1） and Zn（dib）（UO2）F4-0.5H20 （2）. Compound 1 consists of chains of edge-sharing UO2F5 and UO2F4（H20） pentagonal bipyramids, which are linked by Zn（bpi）2 moieties to form the sheet structure with decorated bpi. While in compound 2, sheets of edge- sharing dimers of UO2F5 pentagonal bipyramids and ZnF3N2 polyhedra are linked by dib, creating a pillared three-dimensional framework. The two compounds represent the few examples of heterometallic uranium oxyfluorides incorporating organic ligands. The syntheses, structure as well as the IR spectra, UV-vis spectra and luminescent properties of the bimetallic uranium oxyfluorides are studied.展开更多
The X-ray crystal structure of [(dtma)ZnImZn(dtma)]ClO_4·2.5H_2O (Hdtma=4-Diethyl- enetriamineacetic acid) was determined.The crystal is of orthorhombic,space group Pbcn with a- 14.104(5),b=14.897(5),c=25.384(9),...The X-ray crystal structure of [(dtma)ZnImZn(dtma)]ClO_4·2.5H_2O (Hdtma=4-Diethyl- enetriamineacetic acid) was determined.The crystal is of orthorhombic,space group Pbcn with a- 14.104(5),b=14.897(5),c=25.384(9),and Z=8.The least-square refinement of the structure leads to conventional R factor of 0.066.The magnetic properties of [(dtma)CulmZn(dtma)]CIO_4·2.5H_2O were investigated.From the single crystal ESR spectra of Zn—Im—Zn dimer doped with Cu—Im—Zn complex,the anisotropic g and A tensors and electronic spin-density of the Cu—Zn complex are obtained and the bonding nature of Cu is discussed.展开更多
A new imidazolate bridged Cu^(2+),Zn^(2+)binuclear complex[(dtma) CulmZn (dtma)]ClO_4· 2.5H_2O taken as active site model for Cu,Zn-SOD has been synthesized and its crystal structure determined.All the bond lengt...A new imidazolate bridged Cu^(2+),Zn^(2+)binuclear complex[(dtma) CulmZn (dtma)]ClO_4· 2.5H_2O taken as active site model for Cu,Zn-SOD has been synthesized and its crystal structure determined.All the bond lengths, bond angles and the distance between Cu and Zn atoms in Cu-Im- Zn core of the model complex are close to those in Cu,Zn-SOD.ESR parameters of the model complex as a function of pH show that the imidazolate bridge is stable in pH range 10—12,and is broken on Zn side at pH～9.With decreasing pH,the imidazole is released at pH～4 and the dtma ligand dissociates from the Cu containing fragment at pH～2.4.展开更多
基金supported by National Nature Science Foundation of China (Nos.21301168,21171162 and U1407101)Jilin Province Youth Foundation (Nos.20130522123JH and 20130522132JH)
文摘Two heterometallic uranium oxyfluorides with hybrid networks were hydrothermally synthesized by incorporating two imidazoles, 1-（biphenyl-4-yl）-lH-imidazole （bpi） and 1,4-di（1H-imidazol-l-yl）ben- zene （dib）, formulated as Zn（bpi）2（UO2）2（H2O）F6 （1） and Zn（dib）（UO2）F4-0.5H20 （2）. Compound 1 consists of chains of edge-sharing UO2F5 and UO2F4（H20） pentagonal bipyramids, which are linked by Zn（bpi）2 moieties to form the sheet structure with decorated bpi. While in compound 2, sheets of edge- sharing dimers of UO2F5 pentagonal bipyramids and ZnF3N2 polyhedra are linked by dib, creating a pillared three-dimensional framework. The two compounds represent the few examples of heterometallic uranium oxyfluorides incorporating organic ligands. The syntheses, structure as well as the IR spectra, UV-vis spectra and luminescent properties of the bimetallic uranium oxyfluorides are studied.
文摘The X-ray crystal structure of [(dtma)ZnImZn(dtma)]ClO_4·2.5H_2O (Hdtma=4-Diethyl- enetriamineacetic acid) was determined.The crystal is of orthorhombic,space group Pbcn with a- 14.104(5),b=14.897(5),c=25.384(9),and Z=8.The least-square refinement of the structure leads to conventional R factor of 0.066.The magnetic properties of [(dtma)CulmZn(dtma)]CIO_4·2.5H_2O were investigated.From the single crystal ESR spectra of Zn—Im—Zn dimer doped with Cu—Im—Zn complex,the anisotropic g and A tensors and electronic spin-density of the Cu—Zn complex are obtained and the bonding nature of Cu is discussed.
文摘A new imidazolate bridged Cu^(2+),Zn^(2+)binuclear complex[(dtma) CulmZn (dtma)]ClO_4· 2.5H_2O taken as active site model for Cu,Zn-SOD has been synthesized and its crystal structure determined.All the bond lengths, bond angles and the distance between Cu and Zn atoms in Cu-Im- Zn core of the model complex are close to those in Cu,Zn-SOD.ESR parameters of the model complex as a function of pH show that the imidazolate bridge is stable in pH range 10—12,and is broken on Zn side at pH～9.With decreasing pH,the imidazole is released at pH～4 and the dtma ligand dissociates from the Cu containing fragment at pH～2.4.
