Synthesis, crystal structure, spectroscopy and electroluminescence of zinc(II) complexes containing bidentate 2-(2-pyridyl)quinoline derivative ligands

Three bidentate ligands, 4-phenyl-2-(2-pyridyl)-quinoline (ppq), 6-(carbazol-9-yl)-4-phenyl-2-(2-pyridyl)-quinoline (cpq) and 6-diphenylamino-4-phenyl-2-(2-pyridyl)-quinoline (dpq) and their zinc(II) complexes, have been designed and synthesized. The crystal structure of [Zn(ppq)(2)Cl]PF6 shows that the central zinc atom is coordinated with one chloride and four nitrogen atoms from two ligands. The introduction of an electron-donating substituent such as carbazole or an aromatic amine group at the 6-position of the quinoline moiety can generate colored tunable Zn complexes, and the photoluminescence (PL) wavelength was modulated from 418 nm for [Zn(ppq)(2)Cl]PF6 to 591 nm for [Zn(cpq)(2)Cl]PF6 and 638 nm for [Zn(dpq)(2)Cl]PF6 in CH2Cl2 solution. The electroluminescence spectrum of [Zn(dpq)(2)Cl]PF6 exhibits pure red light emission with the Commission Internationale de L'Eclairage (CIE) coordinates (0.63, 0.36) and a maximum at 648 nm.

The synthesis and crystal structure of vanadium complexes: [(VO2)-O-IV(phen)(2)]center dot 6H(2)O and [2,2 '-(bipy)(2)(VO2)-O-V](H2BO3)center dot 3H(2)O

The organic-inorganic hybrid materials vanadium oxide [(VO2)-O-IV(phen)(2)](.)6H(2)O (1) and [(2,2'-bipy)(2)(VO2)-O-V](H2BO3)(.)3H(2)O (2) have been conventional and hydrothermal synthesized and characterized by single crystal X-ray diffraction, elemental analyses, respectively. Although the method and the ligand had been used in the syntheses of the compounds (1) and (2) are different, they almost possess similar structure. They all exhibit the distorted octahedral [VO2N4] unit with organonitrogen donors of the phen and 2,2'-bipy ligands, respectively, which coordinated directly to the vanadium oxide framework. And they are both non-mixed-valence complexes. But the compound (1) is isolated, and the compound (2) consists of a cation of [(2,2'-bipy)(2)(VO2)-O-V](+) and an anion of (H2BO3)(-). So the valence of vanadium of (1) and (2) are tetravalence and pentavalence, respectively. Meanwhile it is noteworthy that pi-pi stacking interaction between adjacent phen and 2,2'-bipy groups in compounds I and 2 also play a significant role in stabilization of the structure. Thus, the structure Of [(VO2)-O-IV(phen)(2)](.)6H(2)O and [(2,2'-bipy)(2)(VO2)-O-V](H2BO3)(.)3H(2)O are both further extended into interesting three-dimensional supramolecular.

Analysis of 2D-nuclear magnetic resonance for Ru(2,2 '-bipyridine)(2)(4,4 '-dimethyl-2,2 '-bipyridine) (PF6)(2)

The H-1 and C-13 NMR spectra are reported for Ru(2,2'-bipyridine)(2)(4,4'-dimethyl-2,2'-bipyridine)(PF6)(2) that may be used as elechochemiluminescent species. Because of the effect of Ru atom on ligands and complex steric configuration, it is, difficult to attribute the spectra of the title molecular. By using 2D H-1-H-1 COSY and H-1-C-13 COSY methods, the proton and carbon-13 spectra are assigned completely. This also provides a basis for NMR characterization of the-similar new compounds.

六氟磷酸二(2,2’-联吡啶)·(4,4’-二甲基-2,2’-联吡啶)合钌(Ⅱ)的二维核磁共振谱分析

用一维NMR方法研究了电化学发光物质六氟磷酸二(2,2’-联吡啶)·(4,4’-二甲基-2,2’-联吡啶)合钌(Ⅱ)的立体结构,借助二维~1H-~1H COSY和~1H-~(13)C COSY实验技术对其氢谱和碳谱进行了完全的归属,并给出了其氢谱和碳谱的化学位移值.

EFFECT OF CRYSTAL-FIELD AND BONDING PROPERTIES ON SPECTRAL STRUCTURE OF EU-2+

Five Eu~(2+)-doped simple fluorides and six Eu~(2+)-doped complex fluorides are synthesized by solid reactions. The strength of the crystal-field at the sites of Eu~(2+) ion, and the degroe of covalenco of Eu—F bond in these hosts are discussed. The f-f transition emission of Eu~(2+) ion is observed in the hosts which has lower coordination number and strong crystal-field. The f-f transition emission of Eu~(2+) ion is observed for the first time in the simple fluoride AlF_3.

晶场效应和化学键性质对Eu~(2+)光谱结构的影响

合成了掺Eu~(2+)的单一氟化物五种和复合氟化物六种;研究了Eu~(2+)在基质中的跃迁发射随晶场、化学键性质变化的规律,在一些低配位数、强晶场的体系中观察到了Eu~(2+)的f→F跃迁发射,首次在室温下,观察到单一氟化物AlF_3:Eu~+中的t→f跃迁发射。