两个由醋酸根和含吡啶基配体构筑的Zn(II)配聚物的合成、晶体结构及其荧光性质

以醋酸锌、异烟肼（INH）、2-氨基吡啶（2-APy）为原料在N,N-二甲基甲酰胺（DMF）溶液中合成了2个Zn（Ⅱ）配位聚合物[Zn（CH₃COO）₂（INH）]_n（1）,[Zn（CH₃COO）₂（2-APy）]_n（2）,用红外光谱、元素分析、粉末X射线衍射、X射线单晶衍射对配合物进行了表征。晶体结构测试表明,配聚物1属单斜晶系,空间群P2₁/c,晶胞参数：a=0.914 44（17）nm,b=0.161 86（3）nm,c=0.871 75（16）nm,β=96.181（3）°,V=1.282 8（4）nm³,Z=4;配聚物为2D层状结构,该层状结构通过氢键弱相互作用,进一步形成3D超分子结构。配聚物2属三斜晶系,空间群P1,晶胞参数：a=0.747 0（4）nm,b=0.814 5（5）nm,c=1.895 7（11）nm,α=88.276（8）°,β=86.202（8）°,γ=84.334（8）°,V=1.144 9（11）nm³,Z=2;配聚物2为一维zig-zag链状结构。室温固态荧光测试显示,配聚物1、2分别在最大波长382.6和367.5 nm处具有较强的荧光发射。     

蓝色有机电致发光材料及器件的研究进展

有机电致发光器件因在全彩平板显示和固态照明领域中具有广阔的应用前景, 而受到人们的广泛关注。 时至今日, 与现有的红色和绿色有机电致发光材料和器件相比, 具有优越综合性能的蓝色有机电致发光材料和器件却始终匮乏。 相对而言, 蓝光材料具有较宽的能隙, 因而很难获得低电压、高效率和良好稳定性的深蓝光器件。 通常, 白色有机电致发光器件可以通过混合三基色或者两种颜色的方法获得。 但是无论哪种方法, 蓝光材料均是必不可少的。 另外, 还可以通过能量传递将蓝光转化为红光和绿光。 因此, 研发出具有优越综合性能的蓝光材料对有机电致发光器件的推广及应用十分关键。 本文综述了近年来蓝色荧光材料、蓝色磷光材料的研究进展以及蓝光材料在蓝色和白色有机电致发光器件中的应用, 并结合现有工作, 对蓝色有机电致发光材料的研究和应用前景进行展望。     

Enhancement of Oxidative Stability of Polyfluorenes for Direct Thermal Lithography

A homopolymer of 9,9′‐bis[4‐(2‐(2‐tetrahydropyranyloxy)ethoxy)phenyl]fluorene and its copolymers with 3,4‐benzothiadiazole and 4,7‐di(3(4‐n‐octylphenyl)‐2‐thienyl)‐2,1,3‐benzothiadiazole were synthesized to produce a series of thermally reactive blue, green, and red luminescent polymers. Thermolytic removal of the tetrahydropyran (THP) group from polymer films, rendered the films insoluble due to the formation of hydroxyl groups on the termini of side chains. Thermal removal of the THP was lowered by up to 200 °C, when acid is present in the films. These polymers were found applicable to patterning by NIR direct thermal lithography, in conjunction with a NIR dye and thermal acid generator. The presence of the phenyl groups at the 9‐site carbon was found necessary to eliminate fluorenone formation, and enhance the colour purity of the material.

     

Unraveling the Impact of Gold(I)–Thiolate Motifs on the Aggregation‐Induced Emission of Gold Nanoclusters

Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface Au^I‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au₁₀SR₁₀], [Au₁₅SR₁₃], [Au₁₈SR₁₄], and [Au₂₅SR₁₈]^?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the Au^I‐SR motifs on the NC surface. Decreasing the length of Au^I‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au⁰‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.     

硼离子对铕掺杂SiO2干凝胶发光性能的影响

采用溶胶-凝胶法制备了Al单掺和B，Al共掺的Eu掺杂SiO2干凝胶。利用荧光光谱、IR，XRD，DSC，TG／DTG等技术研究了硼离子、退火温度对样品发光性质的影响。经500℃以上退火处理用248nm激发的样品，产生Eu^3＋离子^5D0→^7FJ的特征发射，^5D0→^7F1的跃迁分裂为两个峰。比较615nm处的发光强度，掺硼酸样品的发光强度是不加硼酸发光强度的3．3倍。这是因为B离子的加入，在材料中形成了Si—O—B键，破坏了网络的对称性，加强了Eu^3＋的红光发射。当退火温度上升到850℃用350nm激发时，样品有很强的Eu^2＋蓝光发射。Al单掺的发射中心在437nm处，发射半峰宽约为70nm，而B，Al共掺样品的发光中心蓝移到425nm处，单掺样品的蓝光强度几乎是共掺样品强度的2倍。这是由于硼酸的加入改变了基质的网络结构，从而导致单掺和共掺样品发射峰位和强度的改变。     

An X‐shaped π‐conjugated polymer comprising of fluorene units and anthracene units with high efficiency. Synthesis and optical and electrochemical properties

A new X‐shaped π‐conjugated monomer comprising of fluorene units and anthracene units was synthesized, and it was used to fabricate the new X‐shaped π‐conjugated polymers and investigate the properties of the new polymers. Using different molar ratios between such monomer and a fluorene monomer gave three polymers that showed higher absolute PL quantum yields than the linear polyfluorene (PF) in the solid state. After thermal annealing at 200 °C for 4 h, the linear PF showed an additional bathochromic emission at about 550 nm, whereas such red‐shifted emission was fully eliminated for the X‐shaped polymers. The electroluminescent devices based on the X‐shaped polymers with a configuration of ITO/PEDOT:PSS/polymer/LiF/Ca/Al displayed blue emission with low turn‐on voltage and high brightness. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5616–5625, 2008     

有机低维结构EL器件的特性

近年来，有机电发光器件已经有了很大进展，寿命也已突破万小时，尽管如此，如何更进一步提高发光效率仍是人们所关注的热点。通过与无机半导体低维结构特性的类比，指出对某些有机材料体系,低维结构同样可以改善器件的性能。     

Synthesis,Crystal Structure and Luminescent Property of a New Copper (Ⅰ) Iodide Complex Based on 3,5-Dimethy1-4-amino-triazole

The title compound, [Cu_4I_4(C_4H_8N_4)_4], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group Pbca, with α =18.1851(10), b = 9.3697(5), c = 19.8034(10)(A), V= 3374.3(3) (A)~3, C_(16)H_(32)Cu_4I_4N_(16), M_r = 1210.34, Z= 4, Dc= 2.383 g/cm~3,μ = 6.183 mm~(-1), F(000) = 2272, S = 1.032, the final R = 0.0309 and wR =0.1180 for 3854 observer reflections (I＞ 2σ(I)). The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms. The luminescent property of 1 was also studied.     

Synthesis,Crystal Structure and Photoluminescence of a Three-dimensional Zinc(Ⅱ) Coordination Polymer with(20~3)_2(20)_3 Topology

The title compound,[Zn2(H2C4BIm)(ox)2]·2H2O(1,H2C4BIm = 2,2'-(1,4-bu-tanediyl)bis(1H-benzimidazole),has been synthesized by the hydrothermal reaction of Zn(NO3)2·6H2O with H2C4BIm and Na2C2O4 in water solution.It crystallizes in the triclinic system,space group P1 with a = 9.445(9),b = 9.598(9),c = 14.962(14) ,α = 72.160(10),β = 79.905(12),γ = 83.680(11)°,Mr = 633.18,V = 1269(2) 3,Z = 2,Dc = 1.657 g/cm3,F(000) = 644,μ = 1.953 mm-1,the final R = 0.0671 and wR = 0.1689.X-ray crystal structure analysis revealed that 1 is a 3D network with(203)2(20)3 topology in which the ZnII atom can be considered as a 3-connected node and both ox2-and H2C4BIm serve as the linear linkers.