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
The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is u...The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu（Ⅰ）2（3b）（MeCN）2]（CIO4）2 and O2 under mild conditions, which are found to be more efficient than that already reported.展开更多
Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-...Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.展开更多
The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crys...The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).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 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
A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type l...A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.展开更多
A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoc...A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].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
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
High response organic ultraviolet photodetectors（UV-PDs） were demonstrated with 4,4＇,4”- tris[3-methyl-pheny（phenyl）amino]triphenylamine（m-MTDATA） and two Re（Ⅰ） complexes, （bathocuproine）- Re（CO）3CI（Re...High response organic ultraviolet photodetectors（UV-PDs） were demonstrated with 4,4＇,4”- tris[3-methyl-pheny（phenyl）amino]triphenylamine（m-MTDATA） and two Re（Ⅰ） complexes, （bathocuproine）- Re（CO）3CI（Re-BCP） and （bathophenanthroline）Re（CO）3Cl（Re-Bphen） to act as the electron donor and acceptor, re- spectively. UV-PDs have the configuration of indium tin oxide（ITO）/m-MTDATA（25 nm）/m-MTDATA：Re-complex （25-35 nm）/Re-complex（20 nm）/LiF（l nm）/Al（200 nm） with different blend layer thicknesses of 25, 30 and 35 nm. The optimized PD based on Re-Bphen offers a corrected-dark photocurrent up to 760μA/cm^2 at -10 V, corresponding to a response of 310 mA/W which is among the best values reported for organic UV-PDs. Excellent electron transport ability makes for such high photo-to-electron conversion.展开更多
One binuclear sodium（Ⅰ） complex [Na2（2-benzoylbenzoato）4（Phen）2（H2O）2]·H2O has been synthesized with 2-benzoylbenzoic acid and 1,10-henanthroline as ligands. The crystal structure was determined by X-ray...One binuclear sodium（Ⅰ） complex [Na2（2-benzoylbenzoato）4（Phen）2（H2O）2]·H2O has been synthesized with 2-benzoylbenzoic acid and 1,10-henanthroline as ligands. The crystal structure was determined by X-ray diffraction. The crystal belongs to the triclinic system with space group P , a = 1.08096（8）, b = 1.09619（8）, c = 1.09740（8） nm, α = 79.0600（1）, β = 71.0450（1）, γ = 62.0540（1）o, V = 1.08533（1） nm3, Dc = 1.421 g/cm3, Z = 2, F（000） = 484, GOOF = 1.036, the final R = 0.0363 and wR = 0.0961. The crystal structure shows that two neighboring sodium（Ⅰ） ions are linked together by two bridging water molecules, and each end position is coordinated with one 1,10-phenanthroline molecule and one 2-benzoylbenzoato to form a binuclear structure. Each sodium（Ⅰ） ion in the molecule is coordinated with five atoms to give a distorted trigonal bipyramid. The fluorescence property of the title complex is also discussed.展开更多
A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffrac...A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a = 7.4782（14）, b = 10.1400（11）, c = 16.6982（14） , α = 103.494（11）, β = 91.996（13）, γ = 103.829（12）o, C26H32Cl2N2Rh2, Mr = 649.26, V = 1190.0（3）3, Dc = 1.812 g/cm3, Z = 2, F（000） = 652, μ（Mo Kα） = 1.629 mm-1, R = 0.0286 and w R = 0.0463 for 3718 observed reflections（I 2σ（I））. The complex was linked to form 1D chains by hydrogen bonding interaction（C–H···Cl）, and further to construct a 2D layer structure by π···π stacking interactions between the pyridine rings of 2,2＇-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.展开更多
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the support from the National Natural Science Foundation of China(No.20172038).
文摘The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu（Ⅰ）2（3b）（MeCN）2]（CIO4）2 and O2 under mild conditions, which are found to be more efficient than that already reported.
基金the State Key Project (No. 2005CCA06800)the NSFC/RGC Joint Research Foundation (50418010)
文摘Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.
文摘The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).
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 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.
文摘A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.
文摘A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].
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.
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.60978059)the Program for New Century Excellent Talents in Universities of China(No.NCET-10-0176)+1 种基金the Key Project of Ministry of Education of China(No.210053)the Natural Science Foundation of Jilin Province,China(Nos.20101543 and 20100549)
文摘High response organic ultraviolet photodetectors（UV-PDs） were demonstrated with 4,4＇,4”- tris[3-methyl-pheny（phenyl）amino]triphenylamine（m-MTDATA） and two Re（Ⅰ） complexes, （bathocuproine）- Re（CO）3CI（Re-BCP） and （bathophenanthroline）Re（CO）3Cl（Re-Bphen） to act as the electron donor and acceptor, re- spectively. UV-PDs have the configuration of indium tin oxide（ITO）/m-MTDATA（25 nm）/m-MTDATA：Re-complex （25-35 nm）/Re-complex（20 nm）/LiF（l nm）/Al（200 nm） with different blend layer thicknesses of 25, 30 and 35 nm. The optimized PD based on Re-Bphen offers a corrected-dark photocurrent up to 760μA/cm^2 at -10 V, corresponding to a response of 310 mA/W which is among the best values reported for organic UV-PDs. Excellent electron transport ability makes for such high photo-to-electron conversion.
基金Supported by the Fund of Science and Technology Committee of Hunan Province(No.2012GK3030)the Scientific Research Fund of Hunan Provincial Education Department(No.B21018)+2 种基金the Hengyang Bureau of Science & Technology(No.2011kG28)the Science Technology Foundation of Hunan Province(No.2012FJ3020)the Natural Science Foundation of Hunan Province(No.12JJ6013)
文摘One binuclear sodium（Ⅰ） complex [Na2（2-benzoylbenzoato）4（Phen）2（H2O）2]·H2O has been synthesized with 2-benzoylbenzoic acid and 1,10-henanthroline as ligands. The crystal structure was determined by X-ray diffraction. The crystal belongs to the triclinic system with space group P , a = 1.08096（8）, b = 1.09619（8）, c = 1.09740（8） nm, α = 79.0600（1）, β = 71.0450（1）, γ = 62.0540（1）o, V = 1.08533（1） nm3, Dc = 1.421 g/cm3, Z = 2, F（000） = 484, GOOF = 1.036, the final R = 0.0363 and wR = 0.0961. The crystal structure shows that two neighboring sodium（Ⅰ） ions are linked together by two bridging water molecules, and each end position is coordinated with one 1,10-phenanthroline molecule and one 2-benzoylbenzoato to form a binuclear structure. Each sodium（Ⅰ） ion in the molecule is coordinated with five atoms to give a distorted trigonal bipyramid. The fluorescence property of the title complex is also discussed.
基金Supported by the National Natural Science Foundation of China(Nos.2126102021361022)+2 种基金the Scientific and Technological Landing Project of Higher Education of Jiangxi Province(No.KJLD12094)the College Students’ Innovative Education Program of Jiangxi Provincethe Leading Talent Training Plan of "Xinjiang 866 Engineering Excellence"of Shangrao city
文摘A new complex [Rh（COD）（2,2＇-bipy）]·[Rh（COD）Cl2]（COD = 1,5-cyclooctadiene, 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by elemental analyses, NMR and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1 with a = 7.4782（14）, b = 10.1400（11）, c = 16.6982（14） , α = 103.494（11）, β = 91.996（13）, γ = 103.829（12）o, C26H32Cl2N2Rh2, Mr = 649.26, V = 1190.0（3）3, Dc = 1.812 g/cm3, Z = 2, F（000） = 652, μ（Mo Kα） = 1.629 mm-1, R = 0.0286 and w R = 0.0463 for 3718 observed reflections（I 2σ（I））. The complex was linked to form 1D chains by hydrogen bonding interaction（C–H···Cl）, and further to construct a 2D layer structure by π···π stacking interactions between the pyridine rings of 2,2＇-bipy ligands. The hydroformylation catalyzed by the title complex was also studied.
