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
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
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
There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this produ...There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this product via the oxidation of 4,4′ bismethyl 2,2′ bipyridine, followed by esterification and reduction. The yield increases and the reaction conditions become genial in contrast to those of other methods. The molecular structure of the final product was confirmed by means of elemental analysis, IR, 1H NMR and MS spectra.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
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
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
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 series of novel praseodymium(Pr)-bonded polymers were successfully synthesized via the coordination reaction and palladium-catalyzed Suzuki coupling reaction of 2,7-dibromo-9,9’-dioctylfluorene and different amou...A series of novel praseodymium(Pr)-bonded polymers were successfully synthesized via the coordination reaction and palladium-catalyzed Suzuki coupling reaction of 2,7-dibromo-9,9’-dioctylfluorene and different amounts of 5,5’-dibromo-2,2’-bipyridine. The resulting polymers were characterized by;H-NMR and GPC. The photoluminescence(PL) and electroluminescence(EL) properties of the resulting polymers were studied to explore the effects of the Pr triisopropyloxide. The results showed that the incorporation of Pr into the polymers caused better coplanarity and effective intermolecular or intramolecular interaction, leading to the higher emission intensity at long-wavelength. Further, it was also found that the emission light color could be tuned from blue to green by introduction of a small amount of Pr into the polymer main chain. A single-layer green emitting EL device based on PF(Bipy Pr)6 with 6 mol% Pr content was fabricated. The device had a low turn-on voltage of 6 V, a brightness of 705.3 cd·m;, the maximum luminous efficiency of 1.53 cd·A;and the maximum power efficiency of 0.69 lm·W;.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
Two new hipyridine ligands with intramolecular charge transfer system. (ICT) transition as the lowest excited state were designed and synthesized. Upon addition of metal ions, particularly Zr2+, the absorption and emi...Two new hipyridine ligands with intramolecular charge transfer system. (ICT) transition as the lowest excited state were designed and synthesized. Upon addition of metal ions, particularly Zr2+, the absorption and emission spectra experience great changes. The binding constants towards Zn2+ are 1.27 x 10(5) L/mol and 1.66 x 10(5) L/mol for ligands 1 and 2, respectively. The strong binding affinity and high selectivity make them attractive for application as fluorescence sensors for Zn2+.展开更多
The mono- and binuclear Cu(I) complexes with substituted 2,2'-bipyridine and iodide ligands, [CuL2]BF4 (L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2'-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2'-bipyridine...The mono- and binuclear Cu(I) complexes with substituted 2,2'-bipyridine and iodide ligands, [CuL2]BF4 (L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2'-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2'-bipyridine (b) and 6-(4-methoxylphenyl)-2,2'-bipyridine (c)) and [Cu2(-I)2L2] were prepared, and the crystal structures of the com-plexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nm. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(I) state.展开更多
Two special manganese complexes [Mn(II)(acac )2(4,4'-bipy)]n (bipy=4,4'-bipyridine) (complex 1) and [Mn(II1)(acac-)3].4CO(NH2)2 (acacH=acetylacetone) (complex 2) were synthesized in the same stra...Two special manganese complexes [Mn(II)(acac )2(4,4'-bipy)]n (bipy=4,4'-bipyridine) (complex 1) and [Mn(II1)(acac-)3].4CO(NH2)2 (acacH=acetylacetone) (complex 2) were synthesized in the same strategy by sol- vothermal method. Single crystal X-ray diffraction revealed the complex 1 consists of one-dimensional infinite coordination chain, with the manganese centers bridged by 4,4'-bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14-membered carbamide ring and a zig-zag plane. Both enantiomers of Mn(III)(acac )3 exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig-zag planes are linked with hydrogen bonds to form an unique spatial network.展开更多
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.
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Supported by the National Natural Science Foundation of China(No. 2 0 16 2 0 0 5 ) the Foundation of EducationMinistry(No. 2 0 0 1- 3) .
文摘There are several paths for synthesizing 4,4′ bis(hydroxymethyl) 2,2′ bipyridine, but most of them need strict experimental conditions that are not easy to be overcome. We designed a simple way to prepare this product via the oxidation of 4,4′ bismethyl 2,2′ bipyridine, followed by esterification and reduction. The yield increases and the reaction conditions become genial in contrast to those of other methods. The molecular structure of the final product was confirmed by means of elemental analysis, IR, 1H NMR and MS spectra.
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.
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 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.
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financially supported by the National Natural Science Foundation of China(Nos.21574021 and 51573026)the Natural Science Foundation of Fujian Province(No.2015J01189)+1 种基金the Program for Innovative Research Team in Science and Technology in Fujian Province(IRTSTFJ)the Program of the Education Department of Fujian Province(No.JA14078)
文摘A series of novel praseodymium(Pr)-bonded polymers were successfully synthesized via the coordination reaction and palladium-catalyzed Suzuki coupling reaction of 2,7-dibromo-9,9’-dioctylfluorene and different amounts of 5,5’-dibromo-2,2’-bipyridine. The resulting polymers were characterized by;H-NMR and GPC. The photoluminescence(PL) and electroluminescence(EL) properties of the resulting polymers were studied to explore the effects of the Pr triisopropyloxide. The results showed that the incorporation of Pr into the polymers caused better coplanarity and effective intermolecular or intramolecular interaction, leading to the higher emission intensity at long-wavelength. Further, it was also found that the emission light color could be tuned from blue to green by introduction of a small amount of Pr into the polymer main chain. A single-layer green emitting EL device based on PF(Bipy Pr)6 with 6 mol% Pr content was fabricated. The device had a low turn-on voltage of 6 V, a brightness of 705.3 cd·m;, the maximum luminous efficiency of 1.53 cd·A;and the maximum power efficiency of 0.69 lm·W;.
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.
文摘Two new hipyridine ligands with intramolecular charge transfer system. (ICT) transition as the lowest excited state were designed and synthesized. Upon addition of metal ions, particularly Zr2+, the absorption and emission spectra experience great changes. The binding constants towards Zn2+ are 1.27 x 10(5) L/mol and 1.66 x 10(5) L/mol for ligands 1 and 2, respectively. The strong binding affinity and high selectivity make them attractive for application as fluorescence sensors for Zn2+.
基金Project supported by the National Natural Science Foundation of China (Nos. 50273045,90210033) Chinese Government for support of Chinese Academy of Science Hundred Talents and the foundation for Key Project of Yunnan Provincial Science and Technolo
文摘The mono- and binuclear Cu(I) complexes with substituted 2,2'-bipyridine and iodide ligands, [CuL2]BF4 (L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2'-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2'-bipyridine (b) and 6-(4-methoxylphenyl)-2,2'-bipyridine (c)) and [Cu2(-I)2L2] were prepared, and the crystal structures of the com-plexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nm. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(I) state.
文摘Two special manganese complexes [Mn(II)(acac )2(4,4'-bipy)]n (bipy=4,4'-bipyridine) (complex 1) and [Mn(II1)(acac-)3].4CO(NH2)2 (acacH=acetylacetone) (complex 2) were synthesized in the same strategy by sol- vothermal method. Single crystal X-ray diffraction revealed the complex 1 consists of one-dimensional infinite coordination chain, with the manganese centers bridged by 4,4'-bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14-membered carbamide ring and a zig-zag plane. Both enantiomers of Mn(III)(acac )3 exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig-zag planes are linked with hydrogen bonds to form an unique spatial network.