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
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
Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and...Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.展开更多
The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The compl...The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The complex crystallizes in monoclinic space group C2/c with a=26.785（7）,b=25.654（6）,c=12.277（3）A,β=106.879（5）°,V=8073（4）A^3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm^3,F（000）=4592,Rint=0.0529,T=293（2）K,μ=8.157 mm^（-1）,the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I〉2σ（Ⅰ）.The intramolecular and intermolecular Au¨Au distances are 2.8670（9）and 3.2367（9）A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.展开更多
A cuprous mononuclear copper complex [Cu（adpypz）CH3CNPPh3]BF4·CH2Cl2（1, adpypz = 9,9-dimethyl-10-（6-（3-phenyl-1H-pyrazol-1-yl）pyridin-2-yl）-9,10-dihydroacridine） was synthesized and characterized by Eleme...A cuprous mononuclear copper complex [Cu（adpypz）CH3CNPPh3]BF4·CH2Cl2（1, adpypz = 9,9-dimethyl-10-（6-（3-phenyl-1H-pyrazol-1-yl）pyridin-2-yl）-9,10-dihydroacridine） was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388（4）, b = 13.4569（4）, c = 16.2561（6） ？, α = 97.154（3）, β = 92.187（3）, γ = 114.119（4）°, V = 2235.38（13） ？3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm^3, F（000） = 996, μ = 2.62 mm^–1, GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm（1）, lifetimes 235 μs and quantum yields（ф = 0.279） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence（TADF） at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.展开更多
A four-coordinate mononuclear cuprous complex oCBP-Cu-Pym(1, oCBP =1,2-bis(diphenylphosphine)-nido-carborane, Pym = 2-methyl-6-(1 H-pyrazol-1-yl)pyridine) was synthe-sized and characterized by elemental analysis, NMR,...A four-coordinate mononuclear cuprous complex oCBP-Cu-Pym(1, oCBP =1,2-bis(diphenylphosphine)-nido-carborane, Pym = 2-methyl-6-(1 H-pyrazol-1-yl)pyridine) was synthe-sized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group C2/c with a = 28.4182(8), b =16.2994(4), c = 22.2708(5) ?, β = 127.219(2)°, V = 8214.8(3) ?3, Z = 8, Mr = 766.92, ρcalc = 1.24 g/cm3, F(000) = 3160, μ = 2.30 mm–1, GOOF = 1.063, the final R = 0.0700 and wR = 0.1903 for7158 observed reflections with I > 2σ(I). The Cu(I) ion adopts a highly distorted tetrahedral geometry defined by two nitrogen and two phosphorous atoms. Under UV 365 nm at room temperature, this complex exhibits green emission with maximum emission peak at 516 nm,lifetime 32.4 μs and quantum yield(ф = 0.461) in the solid state. Photophysical investigation suggests that the emission of complex 1 at room temperature was attributed to TADF, which is strongly supported by theoretic calculation.展开更多
A cuprous dinuclear copper complex [PPh_2PAr_2Cu（μ-SCN）_2CuPPh_2PAr_2]（1,PPh_2PAr_2 =（1-bis（2-methylphenyl）-phosphine-2-diphenylphosphino）benzene） was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in...A cuprous dinuclear copper complex [PPh_2PAr_2Cu（μ-SCN）_2CuPPh_2PAr_2]（1,PPh_2PAr_2 =（1-bis（2-methylphenyl）-phosphine-2-diphenylphosphino）benzene） was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225（2）,b = 11.360（2）,c = 13.420（3） ？,α = 95.81（3）,β = 93.45（3）,γ = 113.78（3）°,V = 1410.4（5） ？~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm^3,F（000） = 616,μ = 3.029 mm^（–1）,GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu（I） is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu（μ-SCN）_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_（max）= 478 nm（1）,lifetimes 4.7 μs and quantum yields（ф = 0.43） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ^（1,3）MLCT excited states.展开更多
A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP a...A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.展开更多
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
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
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 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financially supported by the National Natural Science Foundation of China(21302003)the Science and Technology Project of Henan Province(No.182102210200)
文摘Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.
基金financial supports from the NNSFC(20931006,U0934003,and 91122006)the NSF of Fujian Province(2011J01065)
文摘The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The complex crystallizes in monoclinic space group C2/c with a=26.785（7）,b=25.654（6）,c=12.277（3）A,β=106.879（5）°,V=8073（4）A^3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm^3,F（000）=4592,Rint=0.0529,T=293（2）K,μ=8.157 mm^（-1）,the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I〉2σ（Ⅰ）.The intramolecular and intermolecular Au¨Au distances are 2.8670（9）and 3.2367（9）A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.
基金supported by the National Natural Science Foundation of China(51172232)
文摘A cuprous mononuclear copper complex [Cu（adpypz）CH3CNPPh3]BF4·CH2Cl2（1, adpypz = 9,9-dimethyl-10-（6-（3-phenyl-1H-pyrazol-1-yl）pyridin-2-yl）-9,10-dihydroacridine） was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388（4）, b = 13.4569（4）, c = 16.2561（6） ？, α = 97.154（3）, β = 92.187（3）, γ = 114.119（4）°, V = 2235.38（13） ？3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm^3, F（000） = 996, μ = 2.62 mm^–1, GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm（1）, lifetimes 235 μs and quantum yields（ф = 0.279） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence（TADF） at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.
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 oCBP-Cu-Pym(1, oCBP =1,2-bis(diphenylphosphine)-nido-carborane, Pym = 2-methyl-6-(1 H-pyrazol-1-yl)pyridine) was synthe-sized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group C2/c with a = 28.4182(8), b =16.2994(4), c = 22.2708(5) ?, β = 127.219(2)°, V = 8214.8(3) ?3, Z = 8, Mr = 766.92, ρcalc = 1.24 g/cm3, F(000) = 3160, μ = 2.30 mm–1, GOOF = 1.063, the final R = 0.0700 and wR = 0.1903 for7158 observed reflections with I > 2σ(I). The Cu(I) ion adopts a highly distorted tetrahedral geometry defined by two nitrogen and two phosphorous atoms. Under UV 365 nm at room temperature, this complex exhibits green emission with maximum emission peak at 516 nm,lifetime 32.4 μs and quantum yield(ф = 0.461) in the solid state. Photophysical investigation suggests that the emission of complex 1 at room temperature was attributed to TADF, which is strongly supported by theoretic calculation.
基金supported by the National Natural Science Foundation of China(51172232)
文摘A cuprous dinuclear copper complex [PPh_2PAr_2Cu（μ-SCN）_2CuPPh_2PAr_2]（1,PPh_2PAr_2 =（1-bis（2-methylphenyl）-phosphine-2-diphenylphosphino）benzene） was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225（2）,b = 11.360（2）,c = 13.420（3） ？,α = 95.81（3）,β = 93.45（3）,γ = 113.78（3）°,V = 1410.4（5） ？~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm^3,F（000） = 616,μ = 3.029 mm^（–1）,GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I 〉 2σ（I）. The Cu（I） atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu（I） is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu（μ-SCN）_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_（max）= 478 nm（1）,lifetimes 4.7 μs and quantum yields（ф = 0.43） at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ^（1,3）MLCT excited states.
基金supported by the National Natural Science Foundation of China(51172232)
文摘A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.
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.
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.
