Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(dipheny...Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.展开更多
The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.Th...The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.The UV spectra showed that the absorption ability of Tb（m-BrBA）3 was the strongest.However,the fluorescent intensity of Tb（o-BrBA）3 was the weakest.The effect of the molecular structure,the energy level of Tb3＋ and energy transfer efficiency from ligands to Tb3＋ were discussed to explain the experimental results.The results indicated that,due to the large atomic radius of bromine,the steric effect caused by the different substitution bromine on the benzene ring might strongly affect the bond length formed by the coordination atoms and Tb3＋.The longer the bond length was,the lower the efficiency of energy transfer was,and the weaker the fluorescent intensity was.展开更多
A PSII reaction center complex consisting of three polypeptides, D_1, D_2 and Cyt. b_(559), was first purified from broad bean leaves. The complex was fairly active inDCIP photoreduction in the presence of DPC, and sh...A PSII reaction center complex consisting of three polypeptides, D_1, D_2 and Cyt. b_(559), was first purified from broad bean leaves. The complex was fairly active inDCIP photoreduction in the presence of DPC, and showed signal Ⅱs either in the dark or under illumination. The complex also contained manganese atoms. Its Mn^(2+)-EPR intensity decreased by about 40% under continuous illumination and recovered to the original level when the complex was transferred to the dark. The above results indicated that the complex reported here contains all of the PSII electron transport chain components from the secondary donor Z to the stable primary electron acceptor Q_A, and it is possible that the complex contains manganese binding sites. The alternation in dark and illumination can induce reversible valence changes of the manganese atoms in the purified complex.展开更多
基金supported by the Key Project of Science and Technology Plan of Beijing Education Commission(KZ20231002808)。
文摘Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.
基金Project supported by the National Natural Science Foundation of China (50973003)Anhui Science and Technology Program (090518026)+1 种基金Natural Science Foundation of Fuyang Normal College (2011CXY04,2009FSKJ04,2011HJJC02ZD,2011HJJC01ZD,2011HJJC05YB,2011HJJC04YB,2011HJJC03YB,2010FSKJ01ZD)Open fund of State Key Laboratory of Rare Earth Materials Chemistry and Applications (RE201101)
文摘The rare earth complexes Tb（o-BrBA）3,Tb（m-BrBA）3 and Tb（p-BrBA）3 were synthesized using o-,m-,p-bromo benzoic acids（2-bromo benzoic acid,3-bromo benzoic acid and 4-bromo benzoic acid） as ligand,respectively.The UV spectra showed that the absorption ability of Tb（m-BrBA）3 was the strongest.However,the fluorescent intensity of Tb（o-BrBA）3 was the weakest.The effect of the molecular structure,the energy level of Tb3＋ and energy transfer efficiency from ligands to Tb3＋ were discussed to explain the experimental results.The results indicated that,due to the large atomic radius of bromine,the steric effect caused by the different substitution bromine on the benzene ring might strongly affect the bond length formed by the coordination atoms and Tb3＋.The longer the bond length was,the lower the efficiency of energy transfer was,and the weaker the fluorescent intensity was.
基金Project supported by the National Natural Science Foundation of China
文摘A PSII reaction center complex consisting of three polypeptides, D_1, D_2 and Cyt. b_(559), was first purified from broad bean leaves. The complex was fairly active inDCIP photoreduction in the presence of DPC, and showed signal Ⅱs either in the dark or under illumination. The complex also contained manganese atoms. Its Mn^(2+)-EPR intensity decreased by about 40% under continuous illumination and recovered to the original level when the complex was transferred to the dark. The above results indicated that the complex reported here contains all of the PSII electron transport chain components from the secondary donor Z to the stable primary electron acceptor Q_A, and it is possible that the complex contains manganese binding sites. The alternation in dark and illumination can induce reversible valence changes of the manganese atoms in the purified complex.
