用核磁共振方法表征6(8)氨基-3H苯[1,2]氧嗪-1,4-二酮

用一维1HNMR、13CNMR方法研究了6(8)氨基-3H苯[1,2]氧嗪-1,4二-酮的结构,并通过二维1H-1H同核相关谱(COSY)、13C-1H异核相关谱(HMQC)及13C-1H异核远程相关谱(HMBC)进一步确定了该类化合物的1H谱和13C谱中各谱峰的归属,为研究同类化合物表征提供了依据。

Synthesis, characterization, photoluminescent and electroluminescent properties of new conjugated 2,2 '-(arylenedivinylene)bis-8-substituted quinolines

A series of new PPV oligomers containing 8-substituted quinoline, 2,2'-(arylenedivinylene) bis-8-quinoline derivatives, were designed and synthesized via a Knoevenagel condensation reaction of quinaldine, 8-hydroxy-or 8-methoxy-quinaldine with aromatic dialdehydes. These PPV oligomers were characterized by H-1 and C-13-NMR, X-ray diffraction, elemental analysis, UV-visible and fluorescence spectroscopies. The X-ray diffraction investigation showed that there are intermolecular pi...pi interactions in the solid state in 1 and 3. The optical and photoluminescent properties study demonstrated that the emission color of the resulting materials varies from blue to yellow and is dependent on the substituents (pi-donor and pi-acceptor groups) on both sides of the conjugated molecules and the aromatic core in the middle of the conjugated backbones. The electroluminescent devices using compounds 1-4 as the emitters and electron-transporting layers were fabricated with the structure ITO/NPB/emitter/LiF/Al. The best device performance with the maximum brightness of 5530 cd m(-2) and the luminous efficiency of 2.4 cd A(-1) is achieved by using compound 4, with intramolecular charge transfer character, as the emitter; these values represent a more than 5-fold improvement in brightness and efficiency compared to compound 3 without methoxy groups on the phenyl rings.

Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: Synthesis, structure, and fluorescent properties of [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (DNBA=3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo6O192-, has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.

A dinuclear aluminum 8-hydroxyquinoline complex with high electron mobility for organic light-emitting diodes

A dinuclear aluminum 8-hydroxyquinoline complex (DAlq(3)) with improved electron mobility was designed for organic light-emitting diodes. The electron mobility in DAlq(3) was determined via transient electroluminescence (EL) from bilayer devices with structure of indium tin oxide (ITO)/N,N-'-di(naphthalene-1-yl)-N,N-'-diphenyl-benzidine (NPB)/DAlq(3)/Mg:Ag. It was found that the electron mobility in DAlq(3) is between 3.7-8.4x10(-6) cm(2)/Vs at electric fields ranging between 1.2x10(6) and 4.0x10(6) V/cm, which is a factor of two higher than that in Alq(3). The DAlq(3) also shows a higher EL efficiency of 2.2 cd/A (1.2 Lm/W), as compared to Alq(3) with an EL efficiency of 2.0 cd/A (1.0 Lm/W), which is attributed to more balanced electron and hole recombination due to the improved electron mobility of DAlq(3).

用紫外-可见吸收光谱研究微过氧化物酶-8与La~(3+)相互作用机理

首次用紫外-可见(UV-Vis)吸收光谱技术研究了微过氧化物酶-8(MP-8)与La3+的相互作用的机理。发现La3+优先与MP-8分子中血红素卟啉环上的两个丙酸基团的羧基氧发生键合作用,使血红素卟啉环的非平面性增加,π-π跃迁所需要的能量减少,但几率降低。La3+与MP-8肽链上的羰基氧发生弱相互作用,因此对卟啉环的结构基本上没有影响。

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

Infrared spectrum of 2-octadecyl-7,7,8,8-tetracyanoquinodimethane

Infrared spectrum of 2-octadecyl-7,7,8,8-tetracyanoquinodimethane was dealt with 2nd-derivative and deconvolution methods. It was first discovered that the band near 2849 cm(-1) assigned to the CH2 Symmetric stretching mode splited into two bands and this splitting might result from the coexistence of two kinds of conformations of CH2 in the hydrocarbon chain.

Novel bis(8-hydroxyquinoline)phenolato-aluminum complexes for organic light-emitting diodes

A novel series of emitting aluminum complexes containing two 8-hydroxyquinoline ligands (q) and a phenolato ligand (p) were synthesized and characterized. Double layer organic light-emitting diodes (OLEDs) were fabricated using these complexes as luminescent layers, and strong electroluminescence (EL) was observed. It was found that their emitting wavelengths were mainly determined by the first ligands (q). Cyclic voltammograms revealed a partially irreversible n-doping process and indicated that these complexes show excellent electron-transporting ability.

Hydrothermal synthesis and structural characterization of a novel P-V-O layered compound [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)8]

A new compound [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)(8)] has been hydrothermally synthesized. Single crystal X-ray analysis indicates that this compound crystallizes in a monoclinic system, space group P2(1)/n with a=1.438 5(3) nm, b=1.012 2(2) nm, c=1.832 5(4) nm, beta=90.21degrees, V=2.668 2 (9) nm(3), Z = 2, D-c = 2.112 g/cm(3), R = 0.055, wR = 0.149 7, S = 1.037. The structure of [H(2)en](2)[H3O](6)[Co(H2O)(2)(VO)(8)(OH)(4)(PO4)(8)] is characterized by P-V-O layers constructed by [(VO)4 (OH)(2)(PO4)(4)](6-) non-symmetric units. The P-V-O layers are pillared by [Co(H2O)(2)](2+) group, resulting in the channels within which the protonated diaminoethane and H3O+ are located.

Hydrothermal synthesis and crystal structure of a hybrid material based on [Co-4(phen)(8)(H2O)(2)(HPO3)(2)](4+) and a highly reduced polyoxoanion

An unusual composite hybrid material [Co-4 (phen)(8) (H2O)(2) (HPO3)(2)](H3O)(3) [PMo8VI V-4(IV) O-40 ((VO)-O-IV) 2] 1 (phen = 1,10-phenanthroline) has been hydrothermally synthesized from a mixture of NH4VO3, Na2MoO4.2H(2)O, CoCl2.6H(2)O, phen, H3PO3 and water. It was characterized by elemental analysis, IR, UV-vis, XPS, EPR, TG and single crystal X-ray diffraction. The title compound is constructed from the organic-inorganic hybrid [Co-4(phen)(8)(H2O)(2) (HPO3)(2)](4+) and highly reduced bi-capped pseudo-Keggin [(PMo8V4O40)-V-VI-O-IV ((VO)-O-IV)(2)](7-) polyoxoanions The structure exhibits an extended 2D network through hydrogen bonds among cations, anions and H2O, combining polyoxometalates with metal phosphonates for the first time.

New PPV oligomers containing 8-substituted quinoline for light-emitting diodes

Two new poly(phenylenevinylene) (PPV) oligomers, 2,2'-(1,4-phenylenedivinylene)bis-8-acetoxy quinolines were synthesized via a Knoevenagel condensation reaction. The single-crystal X-ray diffraction study shows that there are intermolecular pi...pi interactions in the solid state of 2,2'(1,4-phenylenedivinylene)bis-8-acetoxyquinoline. Electroluminescent properties using these compounds as emitters have been investigated.

Sol-gel deposition and luminescent properties of oxyapatite Ca-2(Y,Gd)(8)(SiO4)(6)O-2 phosphor films doped with rare earth and lead ions

Rare-earth and lead ions (Eu3+, Tb3+, Dy3+, Pb2+) doped Ca2Y8 (SiO4)(6)O-2 and Ca2Gd8(SiO4)(6)O-2 thin films have been dip- coated on silicon and quartz glass substrates through the sol- gel route. X- Ray diffraction (XRD), TG- DTA, scanning electron microscopy (SEM), atomic force microscopy (AFM), FT- IR and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resulting films. The results of XRD reveal that these films remain amorphous below 700 degreesC, begin to crystallize at 800 degreesC and crystallize completely around 1000 degreesC with an oxyapatite structure. The grain structure of the film can be seen clearly from SEM and AFM micrographs, where particles with various shapes and average size of 250 nm can be resolved. Eu3+ and Tb3+ show their characteristic red (D-5(0)-F-7(2)) and green (D-5(4) - F-7(5)) emission in the films with a quenching concentration of 10 and 6 mol% (of Y3+), respectively. The lifetime and emission intensity of Eu3+ increase with the temperature treatment from 700 to 1100 degreesC, while those of Tb3+ show a maximum at 800 degreesC. Energy transfer phenomena have been observed by activating the oxyapatite film host- lattice Ca2Gd8(SiO4)(6)O-2 with Tb3+ (Dy3+). In addition, Pb2+ can sensitize the Gd3+ sublattice in Ca2Gd8(SiO4)(6)O-2.

Synthesis, electrochemistry, and photophysics of a novel binuclear polypyridyl Ru ( II ) complex with an 1,8-adipoylamido-bis(1, 10-phenanthroline-5-yl) ligand

The present paper covers the syntheses of 1,8-adipoylamido-bis(1,10-phenanthroline-5-yl)(bphaa) and its binuclear complex {[(bpy)(2)Ru](2)(bphaa)} (PF6)(4), where bpy is 2,2'-bipyridine. The two novel compounds were confirmed by means of elemental analysis, IR, and LD-MS and H-1 NMR, and H-1 NMR spectra were completely assigned in virtue of H-1-H-1 COSY. chemical behavior of the binuclear Ru (I) complex was obtained using cyclic and voltammetry. Its photophysical property was investigated by electronic absorption, excitation and emission spectra.

Electrochemiluminescence of the Ru(bpy)(3)(2+)/S(2)O(8)(2-)system in purely aqueous solution at carbon paste electrode

The electrochemiluminescence (ECL) of the Ru(bgy)(3)(2-)/S2O82- system in purely aqueous solution at a carbon paste electrode can be clearly seen with the naked eye for Ru(bpy)(3)(2+) concentrations higher than 1 mmol L-1. The log-log plot of the emmitted light intensity vs. Ru(bpy)(3)(2+) concentration is linear over the region 10(-3)-10(-7) mol L-1 with a correlation coefficient of 0.997. The ECL intensity increases linearly with the S2O82- concentration from 10(-6) mol L-1 up to 0.3 mmol L-1 and drops off sharply at concentrations higher than 1 mmol L-1. In addition, a weak ECL signal was obtained when the potential was biased more negative than -0.6 V even in the absence of S2O82-.