A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in...A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.展开更多
A new functionalized heteroleptic iridium complex coordinated with 1-phenylisoquinoline （1-piq） and a functionalized fl-diketone （G1）, Ir（1-piq）2G1, was synthesized and characterized by 1H-NMR, mass spectrometry...A new functionalized heteroleptic iridium complex coordinated with 1-phenylisoquinoline （1-piq） and a functionalized fl-diketone （G1）, Ir（1-piq）2G1, was synthesized and characterized by 1H-NMR, mass spectrometry and elemental analysis. The larger conjugation of the replacement of acetylacetone （acac） by a functionalizedβ-diketonate ligand led to a significant decrease in the HOMO level toward vacuum level, while Ir（1-piq）2G1 and Ir（1-piq）2（acac） showed red phosphorescent emissions of about 620 nm in dichloromethane solution. The phosphorescent polymer light-emitting devices were achieved, with the complexes incorporated with polyfluorene （PFO） as a host polymer doped with 30% of 5-（4-biphenylyl）-2-（4-tert-butylphenyl）-1,3,4-oxadiazole （PBD） as electron transport material. The energy transfer mechanism of the devices was also discussed. The lower EL performance of Ir（1-piq）2G1 is ascribed to the inter-ligand energy transfer, indicating that it is important to control the energy level of the cyclometalated and ancillary ligands.展开更多
To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(...To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(6)](X_(2)pdt=(SCH_(2))_(2)CX_(2),X=Me,H)with aminodiphosphines(Ph_(2)PCH_(2))_(2)NY(Y=(CH_(2))_(2)OH,(CH_(2))_(3)OH)to obtain two new diiron aminophosphine complexes[Fe_(2)(L1)(μ-Me_(2)pdt)(CO)_(5)](1)and[Fe_(2)(L2)(μ-H_(2)pdt)(CO)_(5)](2),where L1=3-[(diphe-nylphosphaneyl)methyl]oxazolidine,L2=3-[(diphenylphosphaneyl)methyl]-1,3-oxazinane.Moreover,the structures of 1 and 2 have been fully confirmed by elemental analysis,spectroscopic techniques,and single-crystal X-ray diffraction.Using cyclic voltammetry(CV),we investigated the electrochemical redox performance and proton reduc-tion activities of 1 and 2 in acetic acid(HOAc).The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H 2 generation in the presence of HOAc.CCDC:2443967,1;2443969,2.展开更多
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.
基金Project(50803008) supported by the National Natural Science Foundation of ChinaProject(2002CB613403) supported by the Ministry of Science and Technology (MOST) of China+1 种基金Project(09JJ6085) supported by the Natural Science Foundation of Hunan Province,ChinaProject(08hjyh02) supported by the Open Project Program of Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education,China
文摘A new functionalized heteroleptic iridium complex coordinated with 1-phenylisoquinoline （1-piq） and a functionalized fl-diketone （G1）, Ir（1-piq）2G1, was synthesized and characterized by 1H-NMR, mass spectrometry and elemental analysis. The larger conjugation of the replacement of acetylacetone （acac） by a functionalizedβ-diketonate ligand led to a significant decrease in the HOMO level toward vacuum level, while Ir（1-piq）2G1 and Ir（1-piq）2（acac） showed red phosphorescent emissions of about 620 nm in dichloromethane solution. The phosphorescent polymer light-emitting devices were achieved, with the complexes incorporated with polyfluorene （PFO） as a host polymer doped with 30% of 5-（4-biphenylyl）-2-（4-tert-butylphenyl）-1,3,4-oxadiazole （PBD） as electron transport material. The energy transfer mechanism of the devices was also discussed. The lower EL performance of Ir（1-piq）2G1 is ascribed to the inter-ligand energy transfer, indicating that it is important to control the energy level of the cyclometalated and ancillary ligands.
文摘To extend a new family of aminophosphine-coordinated[FeFe]-hydrogenase mimics for catalytic hydro-gen(H_(2))evolution,we carried out the ligand substitutions of diiron hexacarbonyl precursors[Fe_(2)(μ-X_(2)pdt)(CO)_(6)](X_(2)pdt=(SCH_(2))_(2)CX_(2),X=Me,H)with aminodiphosphines(Ph_(2)PCH_(2))_(2)NY(Y=(CH_(2))_(2)OH,(CH_(2))_(3)OH)to obtain two new diiron aminophosphine complexes[Fe_(2)(L1)(μ-Me_(2)pdt)(CO)_(5)](1)and[Fe_(2)(L2)(μ-H_(2)pdt)(CO)_(5)](2),where L1=3-[(diphe-nylphosphaneyl)methyl]oxazolidine,L2=3-[(diphenylphosphaneyl)methyl]-1,3-oxazinane.Moreover,the structures of 1 and 2 have been fully confirmed by elemental analysis,spectroscopic techniques,and single-crystal X-ray diffraction.Using cyclic voltammetry(CV),we investigated the electrochemical redox performance and proton reduc-tion activities of 1 and 2 in acetic acid(HOAc).The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H 2 generation in the presence of HOAc.CCDC:2443967,1;2443969,2.
