A new Zn（Ⅱ） complex [Zn（Phen）2（C（12）H6O4N2）（H2O）]·3H2O with 2,2-bipyridine-3,3-dicarboxylic acid and 1,10-phenanthroline（Phen） as ligands was synthesized, and the crystal data are as follows： monocl...A new Zn（Ⅱ） complex [Zn（Phen）2（C（12）H6O4N2）（H2O）]·3H2O with 2,2-bipyridine-3,3-dicarboxylic acid and 1,10-phenanthroline（Phen） as ligands was synthesized, and the crystal data are as follows： monoclinic, space group P2（1/n）, a=12.5581（11）, b=17.3382（17）, c=15.6687（14） , β=110.579（2）o, Mr=731.02, V=3193.9（5） 3, Dc=1.520 g/cm3, Z=4, μ（Mo Kα）=0.833 mm（-1）, F（000）=1508, the final R=0.0431 and w R=0.0936. In the title complex, the central Zn（Ⅱ） ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties were studied. The title complex possesses irreversible electron transfer in the electrode reaction, and it has a strong emission peak in the range of 470505 nm, with the excitation wavelength being 488 nm.展开更多
The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable tempe...The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable temperature magnetic susceptibility.The crystal(C_(32)H_(26)CoN_(12)OS_(2),Mr=717.70)belongs to the orthorhombic,space group Pnna,a=2.21312(16)nm,b=1.40403(10)nm,c=1.14237(8)nm,V=3.5497(4)nm^(3),Z=4,Dc=1.343g·cm^(-3),μ=0.645mm^(-1),F(000)=1476,and final R_(1)=0.0691,wR_(2)=0.1129 for 231 parameters and 1674 observed reflections[I>2.00σ(I)].The Co(Ⅱ)atom is,in a distorted octahedral geometry,coordinated by six nitrogen atoms from two bridging bipy,two monodentate azpy,and two thiocyanate groups.The bridging ligand bipy links Co(Ⅱ)atoms to form the infinite“rod"with terminal coordination azpy ligand acting as sidearms.Unprecedented three parallel interpenetrating two dimensional(4,4)networks and novel infinite triple helices are formed via hydrogen bonding interactions.CCDC:155588.展开更多
Oxidation of alkybenzenes PhCH_2R(R=H, CH_3, C_2H_5 and n-C_3H_7) under 1 atm. of O_2 or air catalyzed by iron(Ⅱ, Ⅲ)-2,2'-bipyridine and 1,10-phenanthroline complexes, affords the aryl-substituted ketones and al...Oxidation of alkybenzenes PhCH_2R(R=H, CH_3, C_2H_5 and n-C_3H_7) under 1 atm. of O_2 or air catalyzed by iron(Ⅱ, Ⅲ)-2,2'-bipyridine and 1,10-phenanthroline complexes, affords the aryl-substituted ketones and alcohols with the conversion of 15.00％～34.58％ containing of 97.60％～99.80％ ketones and alcohols. The turnover numbers of these catalysts are over 3500 mol-cat. ^(-1)for 3.5 h.展开更多
Bipyridine)tetraacid, a new aza-aromatic tetraacid, was synthesizedstarting from diquinoline, and its structure was confirmed by means of mass spectrum and infrared spectrum.
The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inth...The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inthe visible range show weak Cotton effects, which are approximately of mirror image, indicatingthat the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerenechromophores through the molybdenum centers and lead to induced CD effects.展开更多
With an aim to develop novel luminescence materials, europium and terbium complexes of 2, 5-(2-thiophene)-pyridine (TPY), 5, 5′-bis(5-(2, 2′-bithiophene))-2, 5-pyridine (B2TPY) and 5, 5′-bis(5-(2, 2′-bithiophene))...With an aim to develop novel luminescence materials, europium and terbium complexes of 2, 5-(2-thiophene)-pyridine (TPY), 5, 5′-bis(5-(2, 2′-bithiophene))-2, 5-pyridine (B2TPY) and 5, 5′-bis(5-(2, 2′-bithiophene))-2, 2′-bipyridine (B2TBPY) were synthesized, and their luminescence properties were studied. The complexes exhibited ligand-sensitized emission, which was typical of Eu(Ⅲ) and Tb(Ⅲ) ions. The excitation spectra of Eu(Ⅲ) and Tb(Ⅲ) complexes with TPY (or B2TPY or B2TBPY) show similar bands as these with the ligands. It suggests that, the excitation energy is absorbed by TPY or B2TPY or B2TBPY, the energy transfers from its excited single state to its triplet state, and finally transfers from the ligands to Eu(Ⅲ) and Tb(Ⅲ) ions. The luminescence of Eu(Ⅲ) and Tb(Ⅲ) ions in the TPY or B2TPY or B2TBPY complexes indicates that the metal ions are efficiently excited by the absorbed energy from excitation of the ligands.展开更多
The properties of one-photon absorption(OPA),emission and two-photon absorption(TPA)of a bipyridine-based zinc ion probe are investigated employing the density functional theory in combination with response functions....The properties of one-photon absorption(OPA),emission and two-photon absorption(TPA)of a bipyridine-based zinc ion probe are investigated employing the density functional theory in combination with response functions.The responsive mechanism and coordination mode effect are explored.The structural fluctuation is illustrated by molecular dynamics simulation.The calculated OPA and emission wavelengths of the probe are consistent with the experimental data.It is found that the red-shift of OPA wavelength and the enhancement of TPA intensity are induced by the increased intra-molecular charge transfer mechanism upon metal binding.The structural fluctuation could result in the blue-shift of TPA wavelength and the decrease of the TPA cross section.The TPA properties are quite different among the zinc complexes with different coordination modes.The TPA wavelength of the complexes with two ligands is close to that of the probe,which is in agreement with the experimental observation.展开更多
Two novel cyclotriphosphazene derivatives containing 6- （4-hydroxyphenyl）-2,2′-bipyridine （hopbp） side groups, N3 P3 （dobp） 2 （hopbp） 2 （ 1 ） and N3 P3 （dobp） （hopbp） 4 （2） （ dobp = 2,2′-dioxybiphe...Two novel cyclotriphosphazene derivatives containing 6- （4-hydroxyphenyl）-2,2′-bipyridine （hopbp） side groups, N3 P3 （dobp） 2 （hopbp） 2 （ 1 ） and N3 P3 （dobp） （hopbp） 4 （2） （ dobp = 2,2′-dioxybiphenyl）, were synthesized and characterized. These compounds display strong fluorescent emission both in solution and in solid state. Their absorption and emission spectra are sensitive to proton： the addition of HBF4 to the methanol and dichloromethane solution（9： 1, volume ratio） of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum, and the process was also characterized by isosbestic points of absorption spectra at 267, 287 and 313 nm.展开更多
Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthes...Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthesized by hydrothermal reaction and determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic, space group P2/m with a = 4.7740(10), b = 11.039(2), c = 5.6752(14) ?, β = 91.394(9)o, V = 299.00(11) ?3, Z = 1, Dc = 1.731 g/cm3, F(000) = 157 and μ(MoKa) = 0.7107 mm-1. Compound 2 crystallizes in monoclinic, space group P2/n with a = 12.916(2), b = 11.149(1), c = 15.006(2) ?, β =106.642(6)o, V = 2070.3(5) ?3, Z = 2, Dc = 1.510 g/cm3, F(000) = 970 and μ(MoKa) = 0.7107 mm-1. In the structure of compound 1, the metal atom is in a slightly distorted octahedral CuO4N2 geometry surrounded by four O atoms of two NO2 ligands in the equatorial positions and two N atoms from 4,4?-bipyridine ligands in the axial sites, and the 4,4?-bipyridine ligands bridge the neighboring Cu2+ atoms to form polymeric chains in the lattice. Compound 2 has a 2D square-grid network structure. The square grids are superposed on each other to form a channel framework. The square cavity has dimensions of 11.148(2)? ×11.229(3)?. Every two guest 4,4?-bipyridine molecules are clathra- ted in each hydrophobic host cavity and further stabilized by π-π stacking and hydrogen bonding interactions.展开更多
This paper reports the synthesis of host-guest nanocomposite material [Fe(bpy)(3)]Y2+ (where bpy=2,2'-bipyridine) using the flexible ligand method. X-ray diffraction analysis. adsorption technique, and cyclic volt...This paper reports the synthesis of host-guest nanocomposite material [Fe(bpy)(3)]Y2+ (where bpy=2,2'-bipyridine) using the flexible ligand method. X-ray diffraction analysis. adsorption technique, and cyclic voltammetry were used to characterize the material. The results show that [Fe(bpy)(3)](2+) has been entrapped in the supercage of zeolite, its electron transfer is realized by electron hopping of [Fe(bpy)(3)](2+) within the supercage of zeolite.展开更多
The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(...The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(1) A, c=16.032(7) A, β=106.76(3)°,V=3695(3) A^3, Z=8, Dc=1.58g/cm^3, F(000)=1776. Final R and Rw are 0.062 and 0.069, respectively. The local coordination geometry around Cu(I) ion is a distorted tetrahedron. Cu(TTA) are linked with 4,4-bipyridine, forming long chain in the crystal.展开更多
Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry（HRMS）.Four co...Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry（HRMS）.Four compounds T1―T4 exhibit excellent solubility in common solvents and good film forming properties.Quantum chemical calculations show that compounds T1―T4 have asymmetric linear structures and the proper highest occupied molecular orbital（HOMO） levels.The UV-Vis absorption and fluorescence emission spectra of the four compounds in dilute chloroform solutions and on the solid films were measured.It reveals that compounds T1―T4 exhibit similar spectral behavior,suggesting that these compounds can form amorphous state in solid films.The calculated absorption and emission spectra of compounds T1―T4 are in good agreement with experimentally determined ones.Compounds T1―T4 have absolute fluorescence quantum yield above 17% in dilute chloroform solutions.Four compounds possess high glass-transition temperature（T g） exceeding 97 ℃ and the maximum T g is 155.28 ℃ for compound T3.Cyclic voltammetry measurements show that these compounds have proper HOMO levels in a range of-5.01―-5.13 eV for hole injection.The properties of compounds T1―T4 indicate that these compounds are candidates for the application in organic light-emitting devices（OLEDs） as hole-transporting materials（HTMs）.展开更多
A series of 4,4＇-disubstituted-[2,2＇]-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been syn- t...A series of 4,4＇-disubstituted-[2,2＇]-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been syn- thesized and employed in the copolymerization of carbon monoxide （CO） and styrene. The available bipyridine and its derivatives were coordinated with palladium （ II ） acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of t3C NMR, FTIR, differential scanning calo- rimetry （DSC） and element analysis techniques concerning its structure and thermal performance. The effect of dif- ferent electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of co- polymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composi- tion, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2＇-bipyridine ligand（l 356 gSTCO/（gPd · h））, when the molecular weight and polydispersity index of the polyketone are Mn = 8 502, Mw = 1 3440 and Mw/Mn = 1.581, respectively.展开更多
Two novel silver（I） complexes {[Ag（OTf）（PPh3）（4,4＇-bipy）]}∞（1） and {[Ag2-（OTf）2（dppb）3]（CH3CN）4}∞（2）（OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4＇-bipy = 4,4＇-bipyridine, dppb...Two novel silver（I） complexes {[Ag（OTf）（PPh3）（4,4＇-bipy）]}∞（1） and {[Ag2-（OTf）2（dppb）3]（CH3CN）4}∞（2）（OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4＇-bipy = 4,4＇-bipyridine, dppb = bis（diphenylphosphino）butane） have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a = 19.259（2）, b = 9.85070（12）, c = 16.3827（17） A, V = 3108.0（5） A3, C29H23F3N2O3 PSAg, Mr = 675.39, Z = 4, Dc = 1.443 g/cm3, F（000） = 1360, μ = 0.816 mm-1, the final R = 0.0675 and w R = 0.1722 for 3662 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1 with a = 12.9370（11）, b = 13.5261（13）, c = 16.4539（15） A, α = 106.7120（10）, β = 97.3830（10）, γ = 113.027（2）A, V = 2441.2（4）A3, C94H96F6N4O6P6S2Ag2, Mr = 1957.43, Z = 1, Dc = 1.331 g/cm3, F（000） = 1006, μ = 0.605 mm-1, the final R = 0.0717 and w R = 0.1795 for 5128 observed reflections（I 〉 2σ（I））. Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf- anion, two N atoms from two 4,4＇-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf- anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.展开更多
Conjugated homopolymers based on six-member rings,e.g.,polyfluorene,always exhibit blue emission and conjugated homopolymers based on five-member rings,e.g.,polythiophene,can give red emission with low efficiency.In t...Conjugated homopolymers based on six-member rings,e.g.,polyfluorene,always exhibit blue emission and conjugated homopolymers based on five-member rings,e.g.,polythiophene,can give red emission with low efficiency.In this work,we report a series of new conjugated homopolymers based on six-member rings with high-efficiency deep-red emission.The repeating units of the red light emitting homopolymers are double B←N bridged bipyridine(BNBP)with the boron atoms functionalized with diphenyl,borafluorene,and 2,7-di-tert-butyl-borafluorene groups,respectively.The relationship between the chemical structures and the opto-electronic properties of the monomers and the homopolymers has been systematically studied.The three polymers emit pure red light(λ_(max)=656 nm)or deep red light(λ_(max)=693 nm)with fluorescence quantum efficiency in solution higher than 60%.The polymers can be used as the emitters in solution-processed organic light-emitting diodes with red emission and decent device performance.This work indicates a new strategy to design highly efficient light emitting conjugated polymers.展开更多
The title polymeric complex [Cu(C_4H_2O_4)(C_(10)H_8N_2)]_n·2nH_2O wasprepared and its crystal structure was determined by X-ray diffraction methods. The crystal belongsto space group P2_1/c with cell dimensions ...The title polymeric complex [Cu(C_4H_2O_4)(C_(10)H_8N_2)]_n·2nH_2O wasprepared and its crystal structure was determined by X-ray diffraction methods. The crystal belongsto space group P2_1/c with cell dimensions of a = 1.0104(1), b = 1.9952(2), c = 0.7357(2) nm, β=98.38(2)° and Z = 4. The complex forms zig-zag chains along crystallographic axis c via Cu―O(car-boxyl) bond in the apical direction. Each repeated unit consists of a square pyramidal Cu( Ⅱ)centre with one maleate dianion and one 2, 2′-bipyridine forming a basal plane. Adjacent chainslink to each other by H-bonding between carboxyl groups and crystalline water. The distance of0.3482 run between parallel bipyridine rings shows a π- π stacking interaction. The title complexwas also characterized by IR, UV and ESR spectra.展开更多
Recently, there has been considerable attention focused on the binding of metal complexes to DNA. Since the middle 1980s, Barton et al. have found that the chirl octahedral complexes that contain planar aromatic ligan...Recently, there has been considerable attention focused on the binding of metal complexes to DNA. Since the middle 1980s, Barton et al. have found that the chirl octahedral complexes that contain planar aromatic ligands can bind to double-helical DNA stereoselectively, and the chirl intercalator [Ru（phen）<sub>3</sub>]<sup>3+</sup> has been used as the probe to recognize B and Z-form DNA. The photophysical studies indicated that the complexes containing 1, 10-phenanthroline or larger planar aromatic ligands can be intercalated into DNA stereoselectively and the complexes containing smaller ligands such as 2, 2’-展开更多
[Poly(styryl)bipyridine]palladium(O),a polymer-bound hydrogrnation catalyst,was characterized by DRS,ESCA and electron microscopy.This material was used as cata-lyst for the vinylation of ary liodides.It was found tha...[Poly(styryl)bipyridine]palladium(O),a polymer-bound hydrogrnation catalyst,was characterized by DRS,ESCA and electron microscopy.This material was used as cata-lyst for the vinylation of ary liodides.It was found that the catalytic activlty is comparableto that of the homogeneous catalyst and is not remarkably lowered on being used threetimes With this catalyst,a series of substituted stilbenes,cinnamic acids and methylcinnamates was prepared in high yields.展开更多
A new bipyridine fused rhodamine-like chelating ligand and the corresponding transition metal complexes of platinum(Ⅱ)and iridi-um(Ⅲ)have been designed,synthesized and structurally characterized by X-ray crystallogr...A new bipyridine fused rhodamine-like chelating ligand and the corresponding transition metal complexes of platinum(Ⅱ)and iridi-um(Ⅲ)have been designed,synthesized and structurally characterized by X-ray crystallography.Their photophysical properties and acid-or metal ion-promoted spirocarbon ring-opening properties have been investigated.The platinum(Ⅱ)and iridium(Ⅲ)complexes show a drastic color change in solution with Hg^(2+) ions and emergency of an absorption band at around 450-600 nm,assignable to the absorption band of the ring-opened rhodamine-like ligand.The platinum(Ⅱ)complex was suggested to undergo dissociation with Hg^(2+) ion,based on the corresponding absorption titration study.Emission titration studies of iridium(Ⅲ)complexes were found to suffer from the quenching process,probably due to the presence of a lower-lying non-emissive excited state from the ring-opened form of ligand.展开更多
基金Supported by the Open Fund Project of Key Laboratory of Functional Organometallic Materials of Hengyang Normal University(GN15K02)the Science Foundation of Hengyang Normal University(16D06)
文摘A new Zn（Ⅱ） complex [Zn（Phen）2（C（12）H6O4N2）（H2O）]·3H2O with 2,2-bipyridine-3,3-dicarboxylic acid and 1,10-phenanthroline（Phen） as ligands was synthesized, and the crystal data are as follows： monoclinic, space group P2（1/n）, a=12.5581（11）, b=17.3382（17）, c=15.6687（14） , β=110.579（2）o, Mr=731.02, V=3193.9（5） 3, Dc=1.520 g/cm3, Z=4, μ（Mo Kα）=0.833 mm（-1）, F（000）=1508, the final R=0.0431 and w R=0.0936. In the title complex, the central Zn（Ⅱ） ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties were studied. The title complex possesses irreversible electron transfer in the electrode reaction, and it has a strong emission peak in the range of 470505 nm, with the excitation wavelength being 488 nm.
文摘The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable temperature magnetic susceptibility.The crystal(C_(32)H_(26)CoN_(12)OS_(2),Mr=717.70)belongs to the orthorhombic,space group Pnna,a=2.21312(16)nm,b=1.40403(10)nm,c=1.14237(8)nm,V=3.5497(4)nm^(3),Z=4,Dc=1.343g·cm^(-3),μ=0.645mm^(-1),F(000)=1476,and final R_(1)=0.0691,wR_(2)=0.1129 for 231 parameters and 1674 observed reflections[I>2.00σ(I)].The Co(Ⅱ)atom is,in a distorted octahedral geometry,coordinated by six nitrogen atoms from two bridging bipy,two monodentate azpy,and two thiocyanate groups.The bridging ligand bipy links Co(Ⅱ)atoms to form the infinite“rod"with terminal coordination azpy ligand acting as sidearms.Unprecedented three parallel interpenetrating two dimensional(4,4)networks and novel infinite triple helices are formed via hydrogen bonding interactions.CCDC:155588.
文摘The title compound 5 was synthesized in 45% yield by the reaction of compound 3 with a, a-bis (bromomethyl)-2, 2-bipyridine in CH3CN at 70℃ for 24 h.
文摘Oxidation of alkybenzenes PhCH_2R(R=H, CH_3, C_2H_5 and n-C_3H_7) under 1 atm. of O_2 or air catalyzed by iron(Ⅱ, Ⅲ)-2,2'-bipyridine and 1,10-phenanthroline complexes, affords the aryl-substituted ketones and alcohols with the conversion of 15.00％～34.58％ containing of 97.60％～99.80％ ketones and alcohols. The turnover numbers of these catalysts are over 3500 mol-cat. ^(-1)for 3.5 h.
文摘Bipyridine)tetraacid, a new aza-aromatic tetraacid, was synthesizedstarting from diquinoline, and its structure was confirmed by means of mass spectrum and infrared spectrum.
文摘The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inthe visible range show weak Cotton effects, which are approximately of mirror image, indicatingthat the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerenechromophores through the molybdenum centers and lead to induced CD effects.
基金the Natural Science Foundation of China (20674022 ,20774031)the Natural Science Foundation of Guangdong province (B09B2061310)
文摘With an aim to develop novel luminescence materials, europium and terbium complexes of 2, 5-(2-thiophene)-pyridine (TPY), 5, 5′-bis(5-(2, 2′-bithiophene))-2, 5-pyridine (B2TPY) and 5, 5′-bis(5-(2, 2′-bithiophene))-2, 2′-bipyridine (B2TBPY) were synthesized, and their luminescence properties were studied. The complexes exhibited ligand-sensitized emission, which was typical of Eu(Ⅲ) and Tb(Ⅲ) ions. The excitation spectra of Eu(Ⅲ) and Tb(Ⅲ) complexes with TPY (or B2TPY or B2TBPY) show similar bands as these with the ligands. It suggests that, the excitation energy is absorbed by TPY or B2TPY or B2TBPY, the energy transfers from its excited single state to its triplet state, and finally transfers from the ligands to Eu(Ⅲ) and Tb(Ⅲ) ions. The luminescence of Eu(Ⅲ) and Tb(Ⅲ) ions in the TPY or B2TPY or B2TBPY complexes indicates that the metal ions are efficiently excited by the absorbed energy from excitation of the ligands.
基金the Natural Science Foundation of Shandong Province,China(Grant No.ZR2014AM026).
文摘The properties of one-photon absorption(OPA),emission and two-photon absorption(TPA)of a bipyridine-based zinc ion probe are investigated employing the density functional theory in combination with response functions.The responsive mechanism and coordination mode effect are explored.The structural fluctuation is illustrated by molecular dynamics simulation.The calculated OPA and emission wavelengths of the probe are consistent with the experimental data.It is found that the red-shift of OPA wavelength and the enhancement of TPA intensity are induced by the increased intra-molecular charge transfer mechanism upon metal binding.The structural fluctuation could result in the blue-shift of TPA wavelength and the decrease of the TPA cross section.The TPA properties are quite different among the zinc complexes with different coordination modes.The TPA wavelength of the complexes with two ligands is close to that of the probe,which is in agreement with the experimental observation.
基金Supported by the National Natural Science Foundation of China(Nos.50463001and20471066)the State Key Project of China(No.2005CCA06800).
文摘Two novel cyclotriphosphazene derivatives containing 6- （4-hydroxyphenyl）-2,2′-bipyridine （hopbp） side groups, N3 P3 （dobp） 2 （hopbp） 2 （ 1 ） and N3 P3 （dobp） （hopbp） 4 （2） （ dobp = 2,2′-dioxybiphenyl）, were synthesized and characterized. These compounds display strong fluorescent emission both in solution and in solid state. Their absorption and emission spectra are sensitive to proton： the addition of HBF4 to the methanol and dichloromethane solution（9： 1, volume ratio） of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum, and the process was also characterized by isosbestic points of absorption spectra at 267, 287 and 313 nm.
基金This work was supported by the National Natural Science Foundation of China (No. 20173063) the State Key Basic Research and Development Plan of China (001CB108906) and the NSF of Fujian Province (E0020001)
文摘Two new copper coordination polymers [Cu(μ2-4,4?-bipyridine)(NO2)2]n (C10H8- N4O4Cu, Mr = 311.75) 1 and [Cu(μ2-4,4?-bipyridine)2(H2O)2]n?2n(4,4?-bipyridine)?2nClO4?nH2O (C40H38N8O11Cl2Cu, Mr = 941.22) 2 were synthesized by hydrothermal reaction and determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic, space group P2/m with a = 4.7740(10), b = 11.039(2), c = 5.6752(14) ?, β = 91.394(9)o, V = 299.00(11) ?3, Z = 1, Dc = 1.731 g/cm3, F(000) = 157 and μ(MoKa) = 0.7107 mm-1. Compound 2 crystallizes in monoclinic, space group P2/n with a = 12.916(2), b = 11.149(1), c = 15.006(2) ?, β =106.642(6)o, V = 2070.3(5) ?3, Z = 2, Dc = 1.510 g/cm3, F(000) = 970 and μ(MoKa) = 0.7107 mm-1. In the structure of compound 1, the metal atom is in a slightly distorted octahedral CuO4N2 geometry surrounded by four O atoms of two NO2 ligands in the equatorial positions and two N atoms from 4,4?-bipyridine ligands in the axial sites, and the 4,4?-bipyridine ligands bridge the neighboring Cu2+ atoms to form polymeric chains in the lattice. Compound 2 has a 2D square-grid network structure. The square grids are superposed on each other to form a channel framework. The square cavity has dimensions of 11.148(2)? ×11.229(3)?. Every two guest 4,4?-bipyridine molecules are clathra- ted in each hydrophobic host cavity and further stabilized by π-π stacking and hydrogen bonding interactions.
文摘This paper reports the synthesis of host-guest nanocomposite material [Fe(bpy)(3)]Y2+ (where bpy=2,2'-bipyridine) using the flexible ligand method. X-ray diffraction analysis. adsorption technique, and cyclic voltammetry were used to characterize the material. The results show that [Fe(bpy)(3)](2+) has been entrapped in the supercage of zeolite, its electron transfer is realized by electron hopping of [Fe(bpy)(3)](2+) within the supercage of zeolite.
文摘The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(1) A, c=16.032(7) A, β=106.76(3)°,V=3695(3) A^3, Z=8, Dc=1.58g/cm^3, F(000)=1776. Final R and Rw are 0.062 and 0.069, respectively. The local coordination geometry around Cu(I) ion is a distorted tetrahedron. Cu(TTA) are linked with 4,4-bipyridine, forming long chain in the crystal.
基金Supported by the National High-Tech Research and Development Program of China(No.2008AA03A315)the Natural Science Foundation of Tianjin City,China(No.08JCZDJC16900)
文摘Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry（HRMS）.Four compounds T1―T4 exhibit excellent solubility in common solvents and good film forming properties.Quantum chemical calculations show that compounds T1―T4 have asymmetric linear structures and the proper highest occupied molecular orbital（HOMO） levels.The UV-Vis absorption and fluorescence emission spectra of the four compounds in dilute chloroform solutions and on the solid films were measured.It reveals that compounds T1―T4 exhibit similar spectral behavior,suggesting that these compounds can form amorphous state in solid films.The calculated absorption and emission spectra of compounds T1―T4 are in good agreement with experimentally determined ones.Compounds T1―T4 have absolute fluorescence quantum yield above 17% in dilute chloroform solutions.Four compounds possess high glass-transition temperature（T g） exceeding 97 ℃ and the maximum T g is 155.28 ℃ for compound T3.Cyclic voltammetry measurements show that these compounds have proper HOMO levels in a range of-5.01―-5.13 eV for hole injection.The properties of compounds T1―T4 indicate that these compounds are candidates for the application in organic light-emitting devices（OLEDs） as hole-transporting materials（HTMs）.
基金Supported by Tianjin Natural Science Foundation(No.07JCYBJC00600)
文摘A series of 4,4＇-disubstituted-[2,2＇]-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been syn- thesized and employed in the copolymerization of carbon monoxide （CO） and styrene. The available bipyridine and its derivatives were coordinated with palladium （ II ） acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of t3C NMR, FTIR, differential scanning calo- rimetry （DSC） and element analysis techniques concerning its structure and thermal performance. The effect of dif- ferent electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of co- polymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composi- tion, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2＇-bipyridine ligand（l 356 gSTCO/（gPd · h））, when the molecular weight and polydispersity index of the polyketone are Mn = 8 502, Mw = 1 3440 and Mw/Mn = 1.581, respectively.
基金Supported by the National Natural Science Foundation of China(No.21171119)the National High Technology Research and Development Program 863 of China(No.2012AA063201)+3 种基金the Committee of Education of the Beijing Foundation of China(No.KM201210028020)Program for Excellent Talents of Beijing City(No.2010D005016000002)the Beijing Municipal Natural Science Foundation(No.7122015)Scientific Research Base Development Program of the Beijing Municipal Commission of Education
文摘Two novel silver（I） complexes {[Ag（OTf）（PPh3）（4,4＇-bipy）]}∞（1） and {[Ag2-（OTf）2（dppb）3]（CH3CN）4}∞（2）（OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4＇-bipy = 4,4＇-bipyridine, dppb = bis（diphenylphosphino）butane） have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a = 19.259（2）, b = 9.85070（12）, c = 16.3827（17） A, V = 3108.0（5） A3, C29H23F3N2O3 PSAg, Mr = 675.39, Z = 4, Dc = 1.443 g/cm3, F（000） = 1360, μ = 0.816 mm-1, the final R = 0.0675 and w R = 0.1722 for 3662 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1 with a = 12.9370（11）, b = 13.5261（13）, c = 16.4539（15） A, α = 106.7120（10）, β = 97.3830（10）, γ = 113.027（2）A, V = 2441.2（4）A3, C94H96F6N4O6P6S2Ag2, Mr = 1957.43, Z = 1, Dc = 1.331 g/cm3, F（000） = 1006, μ = 0.605 mm-1, the final R = 0.0717 and w R = 0.1795 for 5128 observed reflections（I 〉 2σ（I））. Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf- anion, two N atoms from two 4,4＇-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf- anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.
基金financially supported by the National Natural Science Foundation of China(Nos.22135007 and 52073281)。
文摘Conjugated homopolymers based on six-member rings,e.g.,polyfluorene,always exhibit blue emission and conjugated homopolymers based on five-member rings,e.g.,polythiophene,can give red emission with low efficiency.In this work,we report a series of new conjugated homopolymers based on six-member rings with high-efficiency deep-red emission.The repeating units of the red light emitting homopolymers are double B←N bridged bipyridine(BNBP)with the boron atoms functionalized with diphenyl,borafluorene,and 2,7-di-tert-butyl-borafluorene groups,respectively.The relationship between the chemical structures and the opto-electronic properties of the monomers and the homopolymers has been systematically studied.The three polymers emit pure red light(λ_(max)=656 nm)or deep red light(λ_(max)=693 nm)with fluorescence quantum efficiency in solution higher than 60%.The polymers can be used as the emitters in solution-processed organic light-emitting diodes with red emission and decent device performance.This work indicates a new strategy to design highly efficient light emitting conjugated polymers.
文摘The title polymeric complex [Cu(C_4H_2O_4)(C_(10)H_8N_2)]_n·2nH_2O wasprepared and its crystal structure was determined by X-ray diffraction methods. The crystal belongsto space group P2_1/c with cell dimensions of a = 1.0104(1), b = 1.9952(2), c = 0.7357(2) nm, β=98.38(2)° and Z = 4. The complex forms zig-zag chains along crystallographic axis c via Cu―O(car-boxyl) bond in the apical direction. Each repeated unit consists of a square pyramidal Cu( Ⅱ)centre with one maleate dianion and one 2, 2′-bipyridine forming a basal plane. Adjacent chainslink to each other by H-bonding between carboxyl groups and crystalline water. The distance of0.3482 run between parallel bipyridine rings shows a π- π stacking interaction. The title complexwas also characterized by IR, UV and ESR spectra.
文摘Recently, there has been considerable attention focused on the binding of metal complexes to DNA. Since the middle 1980s, Barton et al. have found that the chirl octahedral complexes that contain planar aromatic ligands can bind to double-helical DNA stereoselectively, and the chirl intercalator [Ru（phen）<sub>3</sub>]<sup>3+</sup> has been used as the probe to recognize B and Z-form DNA. The photophysical studies indicated that the complexes containing 1, 10-phenanthroline or larger planar aromatic ligands can be intercalated into DNA stereoselectively and the complexes containing smaller ligands such as 2, 2’-
文摘[Poly(styryl)bipyridine]palladium(O),a polymer-bound hydrogrnation catalyst,was characterized by DRS,ESCA and electron microscopy.This material was used as cata-lyst for the vinylation of ary liodides.It was found that the catalytic activlty is comparableto that of the homogeneous catalyst and is not remarkably lowered on being used threetimes With this catalyst,a series of substituted stilbenes,cinnamic acids and methylcinnamates was prepared in high yields.
基金the NSFC-CNRS_PRC Joint Research Projects Program(No.21911530232)K.M.C.W.acknowledges the National Natural Science Foundation of China(No.21771099)Science,Technology and Innovation Commission of Shenzhen Municipality(Nos.JCYJ20170817110721105 and JCYJ20190809165411528).
文摘A new bipyridine fused rhodamine-like chelating ligand and the corresponding transition metal complexes of platinum(Ⅱ)and iridi-um(Ⅲ)have been designed,synthesized and structurally characterized by X-ray crystallography.Their photophysical properties and acid-or metal ion-promoted spirocarbon ring-opening properties have been investigated.The platinum(Ⅱ)and iridium(Ⅲ)complexes show a drastic color change in solution with Hg^(2+) ions and emergency of an absorption band at around 450-600 nm,assignable to the absorption band of the ring-opened rhodamine-like ligand.The platinum(Ⅱ)complex was suggested to undergo dissociation with Hg^(2+) ion,based on the corresponding absorption titration study.Emission titration studies of iridium(Ⅲ)complexes were found to suffer from the quenching process,probably due to the presence of a lower-lying non-emissive excited state from the ring-opened form of ligand.
