The vinylidenebis（diphenylphosphine） （vdpp） reacts with CuBr to give a tetranuclear complex, [Cu4（μ3-Br）2（μ2-Br）2（μ2-vdpp）2（CH3CN）2]·（CH3CN）2 1. The title complex has crystallo- graphically impos...The vinylidenebis（diphenylphosphine） （vdpp） reacts with CuBr to give a tetranuclear complex, [Cu4（μ3-Br）2（μ2-Br）2（μ2-vdpp）2（CH3CN）2]·（CH3CN）2 1. The title complex has crystallo- graphically imposed centrosymmetry and presents a CuaBr4 core with distorted stair-like structure. All copper（I） atoms in 1 assume distorted tetrahedral coordination geometry. The distance of 2.7745（11） A between the two copper centers indicates the presence of ligand-supported Cu…Cu interactions. Crystal data for 1： C_60H_56Br_4Cu_4N_4P_4, Mr= 1530.77, triclinic, space group P1, a = 11.6593（9）, b = 11.7181（9）, c = 13.8711（11） А, a = 110.1020（10）, β = 102.0050（10）, γ = 109.8040（10）°, V = 1557.5（2） А^3, Z = 1, Dc = 1.632 g/cm^3, F（000） = 760, λ= 0.71073А, T = 298（2） K, 2θmax = 50.04°,μ= 4.056 mm^-1, S = 1.181, R = 0.0507 and wR = 0.1025.展开更多
Four novel Cu（Ⅰ） complexes,[Cu（o-PYO）（PPh3）2]BF4（1）,[Cu（o-PYO）（DPEphos）]BF4（2）,[Cu2 （o-PYO）（PPh3）3（CH3CN）]（BF4）2（3） and [Cu2（o-PYO）（DPEphos）2 ]（BF4）2（4） （o-PYO=2,5bis（pyridyl）-1,3,4...Four novel Cu（Ⅰ） complexes,[Cu（o-PYO）（PPh3）2]BF4（1）,[Cu（o-PYO）（DPEphos）]BF4（2）,[Cu2 （o-PYO）（PPh3）3（CH3CN）]（BF4）2（3） and [Cu2（o-PYO）（DPEphos）2 ]（BF4）2（4） （o-PYO=2,5bis（pyridyl）-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis（2-（diphenylphosphanyl）phenyl）ether）,have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer （MLCT） absorption bands in the region of 360-480nm.Four Cu（I） complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.展开更多
The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calcula...The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)-Au(Ⅰ) interaction were also discussed.展开更多
A four-coordinate mononuclear cuprous complex [Cu（ac1m）POP]BF4·0.5（C6H14）· 0.5（C2H5OH）（1, ac1 m = 2-（2-ethoxyphenyl）-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, POP = bis[2-（dipenylphosphino）p...A four-coordinate mononuclear cuprous complex [Cu（ac1m）POP]BF4·0.5（C6H14）· 0.5（C2H5OH）（1, ac1 m = 2-（2-ethoxyphenyl）-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, POP = bis[2-（dipenylphosphino）phenyl]ether） was synthesized and characterized by elemental analysis, NMR, UV-vis, cyclic voltammetry and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group P21/c with a = 17.0546（19）, b = 15.4650（17）, c = 23.685（2） A, β = 104.007（11）°, V = 6061.1（12）A^3, Z = 4, Mr = 1171.46, Dc = 1.284 g/cm^3, F（000） = 2432, μ = 1.50 mm^–1, GOOF = 1.070, the final R = 0.059 and wR = 0.1640 for 8952 observed reflections with I 〉 2σ（Ⅰ）. Compound 1 is composed of a BF4-anion and a [Cu（ac1m）POP]^＋ cation. The Cu（Ⅰ） ion adopts a tetrahedral coordination geometry defined by two nitrogen and two phosphorous atoms. The complex exhibits yellow luminescence with maximum emission peaks at 546 nm, lifetimes 15.1 μs and quantum yields（ф = 0.130） at room temperature. The complex displays thermally activated delayed fluorescence（TADF） at room temperature, which is proved experimentally and theoretically. And the organic light-emitting diode（OLED） with 1 as the light emitting material has the maximum current efficiency of 5.86 cd/A and the highest brightness of 3215 cd/m^2.展开更多
Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ...Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a：20,30-c]phenazine） with divalent halogen copper salt CuX2（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl2（dppz）Cu（Ⅰ）Cl]n（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br2（dppz）（DMF）Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.展开更多
Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic ...Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.展开更多
基金Supported by the Open Foundation of Ningbo Municipal Key Laboratory (2007A22003)the National Natural Science Foundation of China (20701022)the Ningbo Municipal Natural Science Foundation (2007A610024)
文摘The vinylidenebis（diphenylphosphine） （vdpp） reacts with CuBr to give a tetranuclear complex, [Cu4（μ3-Br）2（μ2-Br）2（μ2-vdpp）2（CH3CN）2]·（CH3CN）2 1. The title complex has crystallo- graphically imposed centrosymmetry and presents a CuaBr4 core with distorted stair-like structure. All copper（I） atoms in 1 assume distorted tetrahedral coordination geometry. The distance of 2.7745（11） A between the two copper centers indicates the presence of ligand-supported Cu…Cu interactions. Crystal data for 1： C_60H_56Br_4Cu_4N_4P_4, Mr= 1530.77, triclinic, space group P1, a = 11.6593（9）, b = 11.7181（9）, c = 13.8711（11） А, a = 110.1020（10）, β = 102.0050（10）, γ = 109.8040（10）°, V = 1557.5（2） А^3, Z = 1, Dc = 1.632 g/cm^3, F（000） = 760, λ= 0.71073А, T = 298（2） K, 2θmax = 50.04°,μ= 4.056 mm^-1, S = 1.181, R = 0.0507 and wR = 0.1025.
基金supported by the National Natural Science Foundation of China (Nos. 20874098,51073152 and 50772113)the Natural Science Foundation of Fujian Province (No. 2007F3116)
文摘Four novel Cu（Ⅰ） complexes,[Cu（o-PYO）（PPh3）2]BF4（1）,[Cu（o-PYO）（DPEphos）]BF4（2）,[Cu2 （o-PYO）（PPh3）3（CH3CN）]（BF4）2（3） and [Cu2（o-PYO）（DPEphos）2 ]（BF4）2（4） （o-PYO=2,5bis（pyridyl）-1,3,4-oxadiazole,PPh 3=triphenylphosphine,DPEphos=bis（2-（diphenylphosphanyl）phenyl）ether）,have been synthesized and characterized by 1 H NMR,elemental analysis and single-crystal X-ray diffraction.The central cuprous ions in all complexes are surrounded by N and P atoms to form a distorted tetrahedral geometry,although one of the cuprous ions in complex 3 is coordinated by a PPh3 and an acetonitrile molecule due to the steric hindrance and weak coordination ability from monodentate PPh3 ligand.The UV-vis absorption spectra in CH2Cl2 show the characteristic metal-to-ligand charge transfer （MLCT） absorption bands in the region of 360-480nm.Four Cu（I） complexes exhibit yellow to orange-red phosphorescence with the emission maximum at 572,577,562 and 597nm,respectively in the solid state.
文摘The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)-Au(Ⅰ) interaction were also discussed.
基金supported by the National Natural Science Foundation of China(21373221,21521061,51672271,21671190,21403236)the Natural Science Foundation of Fujian Province(2006L2005)
文摘A four-coordinate mononuclear cuprous complex [Cu（ac1m）POP]BF4·0.5（C6H14）· 0.5（C2H5OH）（1, ac1 m = 2-（2-ethoxyphenyl）-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, POP = bis[2-（dipenylphosphino）phenyl]ether） was synthesized and characterized by elemental analysis, NMR, UV-vis, cyclic voltammetry and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group P21/c with a = 17.0546（19）, b = 15.4650（17）, c = 23.685（2） A, β = 104.007（11）°, V = 6061.1（12）A^3, Z = 4, Mr = 1171.46, Dc = 1.284 g/cm^3, F（000） = 2432, μ = 1.50 mm^–1, GOOF = 1.070, the final R = 0.059 and wR = 0.1640 for 8952 observed reflections with I 〉 2σ（Ⅰ）. Compound 1 is composed of a BF4-anion and a [Cu（ac1m）POP]^＋ cation. The Cu（Ⅰ） ion adopts a tetrahedral coordination geometry defined by two nitrogen and two phosphorous atoms. The complex exhibits yellow luminescence with maximum emission peaks at 546 nm, lifetimes 15.1 μs and quantum yields（ф = 0.130） at room temperature. The complex displays thermally activated delayed fluorescence（TADF） at room temperature, which is proved experimentally and theoretically. And the organic light-emitting diode（OLED） with 1 as the light emitting material has the maximum current efficiency of 5.86 cd/A and the highest brightness of 3215 cd/m^2.
基金Supported by the Science and Technology Planning Project of Shengli College China University of Petroleum(No.13070316)
文摘Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a：20,30-c]phenazine） with divalent halogen copper salt CuX2（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl2（dppz）Cu（Ⅰ）Cl]n（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br2（dppz）（DMF）Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.
基金supported by the National Natural Science Foundation of China (No.20872057)
文摘Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.
