电致发光金属配合物和有机小分子的合成与性能

本文以调控发光颜色、提高发光效率为目的，通过改变配体、中心金属离子、取代基等进行颜色调节；通过引入电子或空穴传输单元，实现发光分子的功能化进而改善载流子传输提高发光效率。文中主要以有机小分子和金属配合物为研究对象，它们本身都具有良好的发光性质。工作集中围绕以下几个问题展开：1、PPV齐聚物是一类高效发光的分子体系，如果在其中嵌入8一取代的哇琳单元对发光会有什么影响？2、使用含噁二唑（具有电子传输功能）的配体得到的金属配合物是否能同时拥有双重功能，即高效发光（金属配合物的特点）和优良的电子传输？3、由N2O-双齿配体转变成N，N-双齿配体，配合物的发光又会如何？4、稀土配合物具有高的光致发光效率，但电致发光效率非常低，能否通过咔哇或呛二吟功能化来改善载流子传输，提高电致发光效率？主要工作及取得的结果概述如下：1、经由Knoevenagel缩合反应合成了一系列共骊的2，21-（1，4-芳二乙烯基）双-8-取代喹啉。单晶X-射线衍射研究表明固态下存在分子间，π…π堆积相互作用，这对于载流子传输是比较有利的。喹啉8-位于的取代基的变化对发光影响不大，表明刚性共扼骨架对发光起主要贡献。改变中心的芳核，明显可以调控发光颜色。当存在分子内电荷转移时，与不存在的相比，发光显著红移。电致发光性质表明这些含双喳琳的PPV齐聚物是良好的发光和电子传输材料。2、存在分子内氢键的化合物2-（2-羟基苯基）-5-苯基-1，3，4-噁二唑（HOXD），具有激发态分子内质子转移（ESIPT）特性。在室温下，用365脚的紫外灯照射时表现强的兰色荧光。室温和低温（77K）下的磷光光谱表明它在固态下具有较强的磷光发射，与理论预测完全一致。多层电致发光器件ITO加PB／HOXD／BCP／Alq3／Mg：Ag最大亮度达到656cd／m2，电流效率为0．37cd／A。当把HoxD掺在cBP中时，亮度和效率都有一定程度的提高，达到870cd／m2和0.82cd／A。3、合成了含有德二哩配体（HOXD）的碱金属配合物MOxD（M=Li，Na，K）。我们发现配合物的发光颜色取决于中心金属离子，LiOXD是一个优良的蓝光材料，半峰宽是65nm，发射峰位在478nm，它也可以作为界面材料使用，起到和LIF相同的作用，即改善电子注入。同时作者首次报道了钠和钾的配合物可以用作发光材料。电致发光性质表明这些配合物是优良的蓝／绿色发光和电子注入／传输材料。4、使用从N双齿配体代替N，O-双齿配体（比如8-羟基喹啉），合成了含有2－（2-羟基喹啉）苯并咪唑的锌、铍和硼配合物。用硼配合物作为发光层的三层器件ITO/NPB/boron-complex／Alq3／LiF／A1所得到的光谱覆盖了从400到750nm的区域，表明获得了一个很好的白色发光。白光分别源于激子和激基复合物发光，由三种成分构成：来自于硼配合物的兰色发光（490nm）；来自于Alq3的发光（535nln）；NPB和BPh2（Pybm）界面形成的激基复合物发光（610nm）。器件最大亮度是110cd／m2最大效率是0.8cd／A。5、设计、合成了咔唑、噁二唑功能化的稀土馆配合物，期望通过改善空穴和电子传输来提高发光效率。含咔哇的配合物的双层器件发光光谱较宽，包括三价铺的特征发射和一个宽峰，可能是咔唑的发光。当使用TPD做空穴传输层时，噁二唑铺配合物的电致发光器件得到纯正明亮的红色发光，器件结构为ITO／TPD（40nm）／（OXD-PyBM）Eu（DBM）3（SOnm）／LiF（Inm）／Al（200m），启动电压为7.8V，在21v时达到最大亮度322cd／m2。亮度为57cd／m2和13．sv时电流效率最大，为1.9cd／A，对应外量子效率是1.7％。高的效率表明通过引入噁二唑基团，配合物的电子传输能力得到明显改善。6、初步研究了三线态发光的铱的金属有机配合物，得到了高亮度、高效率的绿色发光；对8-羟基喹啉锌配合物的高分子化也做了初步探讨。

The synthesis and characterization of novel liquid crystalline, meso-tetra[4-(3,4,5-trialkoxybenzoate)phenyl]porphyrins

Five, novel, meso-tetra[4-(3,4,5-trialkoxybenzoate)phenyl]porphyrins and their metal complexes were synthesized and their molecular structures were confirmed by H-1 NMR, FTIR spectroscopy and elemental analysis. Mesomorphic studies using DSC, polarizing optical microscope and X-ray diffraction revealed that all compounds exhibited thermotropic columnar mesophases over a wide mesophase temperature range and low liquid crystalline-crystal line transition temperature. (c) 2007 Elsevier Ltd. All rights reserved

Constructing channel structures based on the assembly of p-sulfonatocalix[4]arene nanocapsules and [M(bpdo)(3)](2+)(M = Cu, Zn)

Novel channel structures based on [M(bpdo)(3)](2+) and p-sulfonatocalix[4]arene nanocapsules have been established; these are sustained exclusively by charge-assisted pi...pi interactions and sorption experiments show the porous materials have selective guest sorption properties.

Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to Alkynes

The B3LYP hybrid density functional method has been carried Out to Study theoretically the mechanisin of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH3)(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH3)2, and in path C of each reaction, the first step is the PH3 dissociation front Pd(PH3)2 to form monophosphine complex Pd(PH3) For both reactions, path B is favored.

Theoretical studies on the reaction mechanism of palladium(0)-catalyzed addition of thiocyanates to alkynes

The reaction mechanism of the Pd(0)-catalyzed alkyne cyanothiolation reaction is investigated by MP2, CCSD(T) and the density functional method B3LYP. The overall reaction mechanism is examined. The B3LYP results are consistent with the results of CCSD(T) and MP2 methods for the isomerization, acetylene insertion and reductive elimination steps, but not for the oxidative addition step. For the oxidative addition, the bisphosphine and monophosphine pathways are competitive in B3LYP, while the bisphosphine one is preferred for CCSD(T) and MP2 methods.

Efficient white organic light-emitting diodes using europium complex as the red unit

Efficient white organic light-emitting diodes (WOLEDs) using europium complex as the red unit are presented. The WOLEDs were fabricated by using the structure of indium tin oxide (ITO)/N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine (NPB)/4,4-N, N-dicarbazolebiphenyl (CBP) : bis(2,4-diphenylquinolyl-N, C-2) iridium (acetylacetonate) ((PPQ)(2)Ir(acac)) : Eu (III) tris(thenoyltrifluoroacetone) 3,4,7,8-tetramethyl-1,10-phenanthroline (Eu(TTA)(3)(Tmphen))/NPB/2-methyl-9,10-di(2-naphthyl)anthracene (MADN) : p-bis (p-N, N-di-phenyl-aminostyryl)benzene (DSA-Ph)/9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/tris(8-hydroxyquinoline) aluminium (Alq3)/LiF/Al.

Grown-like macrocycle zinc complex derived from beta-diketone ligand for the polymerization of rac-lactide

Enolic Schiff base zinc (II) complex 1 was synthesized. XRD revealed 1 was a novel crown-like macrocycle structure consisted of hexanuclear units of (LZnEt)(6) via the coordination chelation between the Zn atom and adjacent amine nitrogen atom. Further reaction of 1 with one equivalent 2-propanol at RT produced Zn-alkoxide 2 by in situ alcoholysis. Complex 2 was used as an initiator to polymerize rac-lactide in a controlled manner to give heterotactic enriched polylactide. Factors that influenced the polymerization such as the polymerization time and the temperature as well as the monomer concentration were discussed in detail in this paper.

Polymerization of ethylene to branched polyethylene with silica and Merrifield resin supported nickel(II) catalysts with alpha-diimine ligands

Silica and Merrifield resin were used as carriers for the support of alpha-diimine nickel(II) precatalysts for ethylene polymerization. The alpha-diimine ligands containing allyl were modified by introducing the reactive Si-Cl end-group, allowing their immobilization via a direct reaction of the Si-Cl groups with the silanols on silica surface or the hydroxyls on the ethanolamine-modified Merrifield resin. The resulting supported alpha-diimine ligands were characterized by analytical and spectroscopic techniques (NMR and Fr-IR).

Fixation of carbon dioxide into aliphatic polycarbonate, cobalt porphyrin catalyzed regio-specific poly(propylene carbonate) with high molecular weight

Cobalt porphyrin complex ((TPPCoX)-X-III) (TPP = 5, 10, 15, 20-Tetraphenylporphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio-specific copolymerization of propylene oxide and carbon dioxide. A turnover frequency of 188 h(-1) was achieved after 5 h, and the byproduct propylene carbonate was successfully controlled to below 1%, where the obtained poly(propylene carbonate) (PPC) showed number average molecular weight (M-n) of 48 kg/mol, head-to-tail content of 93%, and carbonate linkage of over 99%.

Holmium porphyrin compound liquid crystals: Synthesis and properties

5,10,15,20-Tetra-[(p-alkoxy-m-ethyloxy)phenyl]porphyrin and [5-(p-alkoxy)phenyl-10,15,20-tri-phenyl]porphyrin and their holmium(III) complexes are reported. They display a hexagonal columnar discotic columnar Col(h)) liquid crystal phase and were studied by cyclic voltammetry, surface photovoltage spectroscopy (SPS), electric-field-induced surface photovoltage spectroscopy (EFISPS) and luminescence spectroscopy. Within the accessible potential window, all these compounds exhibit two one-electron reversible redox reactions. Quantum yields of Q band are in the region 0.0045-0.21 at room temperature. The SPS and EFISPS reveal that all the compounds are p-type semiconductors and exhibit photovoltaic response due to pi-pi* electron transitions.

Novel Re(I) dendrimers: synthesis, characterization and theoretical studies

Four novel diimine rhenium(I) carbonyl complexes with the formula [Re(CO)(3)(L) Br], where L = 2-(4-(9H-carbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (P1), 2-(4-(3,6-di-tert-butyl-9H-carbazol-9-yl) phenyl)-1H-imidazo-[4,5-f][1,10] phenanthroline (P2), 2-(4-(6-(9H-carbazol-9-yl)-9H-3,9'-bicarbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (D1), and 2-(4-(3', 6'-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-9H-3,9'-bicarbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (D2), have been successfully synthesized and fully characterized by (HNMR)-H-1, IR, and UV-Vis, etc. The luminescence quantum yields (LQYs) of the parent Re(I) complexes P1 and P2 are 0.13 and 0.16, respectively, which are much higher than the previously reported Re(I) dendrimers. The HOMOs and the LUMOs of P1 and P2 are calculated to be mainly composed of [d(Re) + pi(CO + Br)] and pi*(L) orbital, respectively.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.