基于喹喔啉和吡啶并吡嗪及咔唑和二苯胺衍生物电子给体-受体结构荧光材料的合成和光电性能

通过α-二酮与邻苯二胺、吡啶二胺缩合反应,构建了喹喔啉和吡啶并吡嗪衍生物作为电子受体,分别以二苯胺、咔唑衍生物为电子给体,合成了4个具有电子给体-电子受体结构的氮杂环荧光材料F1~F4。通过低温荧光/磷光光谱、荧光寿命测试,结合密度泛函理论计算可知,F1~F4均为荧光小分子。室温荧光光谱结果表明,利用电子给体和受体的电子效应不同可以调控材料的发光颜色,其中三苯胺相对于苯基咔唑的供电子能力更强,表现为F1比F2、F3比F4红移现象更加明显;而吡啶并吡嗪具有多氮的缺电子结构,与喹喔啉相比共轭程度增加,导致F3比F1、F4比F2发生的斯托克斯位移数值增大。总之,F1~F4的甲苯溶液最大荧光光谱发射峰位于529、464、568和507 nm,荧光寿命分别为12.21、2.61、9.76和6.03 ns,荧光量子效率最高可达98.2%,具有良好的发光性能。将F1~F4发光材料掺杂在主体材料中制备了有机电致发光二极管DF1~DF4。所得器件DF1和DF3性能更好,最大电流效率分别为13.38和11.98 cd·A^-1,且最大外量子效率分别达到4.8%和4.5%。     

喹喔啉类红光热活化延迟荧光材料研究进展

红光材料是显示三基色材料之一, 具有发射能量小、穿透能力强和背景荧光干扰小等优点, 被广泛应用于全彩显示、生物传感和光动力治疗等领域. 红光材料目前存在的问题主要有: (1)跃迁能级小, 其非辐射跃迁速率快, 导致量子效率普遍较低; (2)分子共轭较大, 存在较强的π-π堆积作用, 容易导致荧光淬灭; (3)分子设计需要更大的共轭, 在分子合成上较为困难. 热活化延迟荧光(thermally activated delayed fluorescence, TADF)材料作为具有全新的发光机制的材料能够通过反向系间窜越过程利用三重态激子发射荧光, 极大地提高了量子效率, 因此, 基于TADF机制的红光材料成为了近年来人们研究的热点. 由于结构的特点, 喹喔啉及其衍生物非常适合用来构建红光TADF分子. 从喹喔啉类TADF红光材料的分子结构视角出发, 对红光TADF材料的近年来的研究进行概述, 讨论分子结构对材料性能影响, 并且对其发展进行展望.     

6H-吲哚[2,3-b]并喹喔啉衍生物的合成及荧光性能研究

报道了以7-甲(乙)基靛红(1a,1b)为原料,对其1-烃基化得1-烃基-7-甲(乙)基靛红(2a1-2a5,2b1-2b5)。1a,1b,2a1-2a5,2b1-2b5与邻苯二胺在冰醋酸为溶剂或以水为溶剂,四丁基溴化铵(TBAB)为相转移催化剂,采用改进的工艺进行缩合反应,以70.0%-85.8%的收率合成了一系列结构新颖的含有1,4-二氮杂萘结构的吲哚类化合物3a-3b,3a1-3a5,3b1-3b5。化合物3a1-3a5,3b1-3b5为新化合物,其结构经红外光谱、质谱、核磁氢谱(碳谱)确认。荧光光谱测定表明,化合物3a-3b,3a1-3a5,3b1-3b5具有很好的荧光性能。     

新型喹喔啉-三苯胺衍生物的合成及其对Fe3+的识别性能

以4,4-二溴苯偶酰为原料,经过两步反应得到一种新的喹喔啉-三苯胺衍生物4',4''-（6-溴喹喔啉-2,3-二基）双（N,N-二苯基-[1,1'-联苯] -4-胺）（TP1）。通过¹H NMR、¹³C NMR和HR-MS对其结构进行了表征,并利用紫外-可见吸收光谱和荧光光谱研究了衍生物对Fe³⁺的识别性能。光谱测试结果表明：衍生物溶液与Fe³⁺作用后,296nm处的吸光度出现明显变化,说明TP1能选择性识别Fe³⁺;当Fe³⁺浓度为4～200μmol/L时,TP1吸光度与Fe³⁺浓度呈现良好的线性回归关系(R²=0.9977)。      

1,4-二氧喹喔啉甲醛亚胺的合成和抑菌活性

1;4-二氧喹喔啉甲醛亚胺的合成和抑菌活性;二氧喹喔啉甲醛亚胺;合成;结构表征;抑菌活性     

基于给-受体结构的热活化延迟荧光材料

热活化延迟荧光（TADF）材料由于第一单线态（S₁）与三线态激发态（T₁）之间的能级差较小,使得三线态激子能够有效地系间窜越至单线态发光,实现100%的激子利用率,在有机发光二极管（OLED）等领域得到广泛应用,是目前有机电子学研究的热点之一。基于给-受体（D-A）结构构建TADF材料具有分子设计简便、易于制备、性能优异等特点,引起了人们的普遍关注。本文综述了基于D-A结构设计TADF材料的基本原则,依据给受体构筑单元的不同,概括了各类TADF材料的结构和性能特点以及在器件应用等方面的最新研究进展,最后总结了D-A结构型TADF材料尚存在的问题,并对其未来的关键研究方向进行了分析和展望。     

基于喹喔啉结构的异吲哚啉-1-酮类化合物合成及抗肿瘤活性

本文通过3-溴甲基喹喔啉-2-羧酸乙酯与芳胺或脂肪胺在回流的乙醇中经一步反应简便而有效合成了一系列结构新颖的基于喹喔啉结构的异吲哚啉酮类化合物.采用MTT法初步评价了目标化合物对肺癌细胞株A549和直肠癌细胞株HT29的体外增殖抑制活性.结果 表明,含有卤素(F,Cl,Br,I)取代的化合物7h～7k对这两个细胞株表现...     

2-溴甲基-3-(二溴甲基)喹喔啉的合成研究

以2，3－二（溴甲基）喹喔啉为原料，以N－溴琥珀酰亚胺为溴化试剂合成了2－溴甲基－3－（二溴甲基）喹喔啉（1），1是Diels-Alder环加成反应中形成含杂原子环的C60衍生物的一种重要中间体。通过IR，^1H NMR,^13C NMR,DEPT谱和MS对其进行了结构表征。     

氨基酸的2,3-二甲醛基喹喔啉荧光衍生及高效液相色谱分离分析

将荧光试剂2,3-二甲醛基喹喔啉首次应用到氨基酸的高效液相色谱分离分析中。考察了该荧光试剂与伯胺氨基酸衍生反应的pH值、比例、反应时间等影响因素,确定衍生反应的最佳条件为:100 mmol/L硼砂缓冲液(pH 9.5),二巯基乙醇、衍生试剂与氨基酸的比例为9∶3∶1,室温下反应5 min。采用C18色谱柱,经二元梯度洗脱,荧光检测,17种伯胺蛋白氨基酸得到较好分离。氨基酸的浓度在0.01～1.00 mmol/L范围内与其衍生物峰面积呈较好的线性关系,氨基酸衍生物的检出限为0.02～0.07μg/L。应用该方法对麦冬中游离氨基酸的含量进行测定,结果满意。此方法快速,高效,灵敏度高,精密度好。     

压力和酸响应的四苯乙烯修饰喹喔啉类荧光染料的合成与性质研究

合成了新的给受体型四苯乙烯修饰的喹喔啉衍生物BTPQ、DBTPQ和BTBQ.三个化合物表现出不同程度的聚集诱导发光(AIE)行为,当BTBQ (四苯乙烯单元修饰在喹喔啉的2,3-位)的四氢呋喃溶液中含水量达到90%时,其荧光发射强度增加至原来的54倍.此外,固体BTBQ在三氟乙酸蒸气作用下可由淡黄色变成红色,且其蓝绿色荧光被显著猝灭,可见,它可作为传感材料用于酸蒸气的可视化检测.由于连接在喹喔啉5,8-位上的四苯乙烯单元的空阻作用导致BTPQ和DBTPQ不易被质子化,因此,二者对酸不敏感,但是,它们的固态发光颜色在研磨前后发生了明显变化,如,BTPQ在结晶态时发射蓝色荧光,经研磨变成无定形态后,发射蓝绿色荧光, BTPQ和DBTPQ的压致荧光变色行为在研磨、加热/溶剂熏蒸处理下具有可逆性.     

Synthesis, characterization and electrophosphorescent properties of mononuclear platinum(II) complexes based on 2-phenylbenzoimidazole derivatives

The rational design, synthesis and characterization of five phosphorescent platinum complexes [(C^N)Pt(acac)] [Hacac = acetylacetone, HC^N = 1-methyl-2-(4-fluorophenyl)benzoimidazole (H-FMBI), 1-methyl-2-phenylbenzoimidazole (H-MBI), 1,2-diphenyl-benzoimidazole (H-PBI), 1-(4-(3,6-di-t-butylcarbazol-9-yl))phenyl-2-phenylbenzoimidazole (t-BuCz-H-PBI), and 1-(4-(3,6-di-(3,6-di-t-butyl-carbazol-9-yl))carbazol-9-yl)phenyl-2-phenylbenzoimidazole (t-BuCzCz-H-PBI)] have been discussed. The crystal structure of (MBI)Pt(acac) shows a nearly ideal square planar geometry around Pt atom and the weak intermolecular interactions with π-π spacing of 3.55 Å. All of the complexes emit green phosphorescence from the metal-to-ligand charge-transfer (MLCT) excited state with high quantum efficiency (0.08-0.17) at room temperature. A multilayer organic light-emitting diode (OLED) with (MBI)Pt(acac) as phosphorescent dopant was fabricated using the method of high-vacuum thermal evaporation, which gives a maximum brightness, luminous and power efficiency of 13 605 cd/m², 15.1 cd/A and 4.3 lm/W, respectively. In contrast, the comparable performance can be achieved in the solution-processed OLED based on (t-BuCzPBI)Pt(acac) with a peak brightness, luminous and power efficiency of 13 606 cd/m², 17.5 cd/A and 8.4 lm/W, respectively. The better device efficiency results from the good square plane of central Pt coordination unit and the inhibition of the aggregates due to bulky and rigid t-butylcarbazole dendrons.     

基于Cz-DPP不对称D-A结构新型有机小分子光伏材料的合成与性质

本文设计合成了一系列以咔唑(CZ)和吡咯并吡咯二酮(DPP)为基本结构单元的D-A结构的新型小分子材料,并对其进行了一系列的性能表征.合成的材料以咔唑作为给电子单元,吡咯并吡咯二酮作为吸电子单元,采用三键作为π桥,并引入4-氟苯基、4-氰基苯基和4-甲氧基苯基作为末端取代基团对材料进行修饰.其中材料CZBTDPPF和CZBTDPPO因分别具有1.85和1.79 eV的较窄带隙而分别获得了相对较高的的光电转化效率(1.97%和1.91%).由此可见,引入4-氟苯基和4-甲氧基苯基作为末端取代基团对于延长材料共轭结构、拓宽材料吸收从而实现材料光伏性能的提升具有重要的作用.     

Synthesis,EGFR-TK inhibition and anticancer activity of new quinoxaline derivatives

Abstract

Ethyl 4-substituted-3-oxo-quinoxaline-2-carboxylates 3–5 were obtained via alkylation of ethyl 3-oxo-3,4-dihydroquinoxaline-2-carboxylate (1). Compound 1 was heterocyclized using hydrazines, ethylenediamine, and ethanolamine to give pyrazoloquinoxalines 6, 7, diazepinoquinoxaline 8, and oxazepinoquinoxaline 10. The quinoxaline-2-carboxamides 9, 11, 12 were prepared via condensation of compound 1 with different amines. Compound 1 was thiated using Lawesson’s reagent affording quinoxaline-3-thione 13, in fair yield. In addition, the reaction of 4-methyl-3-oxoquinoxaline 3 with some binucleophiles led to a series of new oxoquinoxaline derivatives 14–18. The molecular structure of compounds 1, 3, and 9 was confirmed by X-ray crystallography.

The anti-proliferative activity showed that among all the tested compounds, compounds 3, (IC₅₀ 2.51?±?3.0, 4.22?±?1.6 and 2.27?±?1.9?µM), 11 (IC₅₀ 1.32?±?2.61, 1.41?±?1.23 and 1.18?±?1.91?µM) and 17 (IC₅₀ 1.72?±?1.32, 1.85?±?0.94 and 1.92?±?4.83?µM) showed noteworthy anti-proliferative effects against the three cancer cell lines, HCT116, HePG2 and MCF7, respectively, compared to the reference drugs doxorubicin (IC₅₀ 1.41?±?0.58, 0.90?±?0.62 and 1.01?±?3.02?µM) and erlotinib (IC₅₀ 1.63?±?0.81, 1.57?±?0.62 and 1.49?±?0.54?µM). Compounds 3 (0.899?nM), 11 (0.508?nM) and 17 (0.807) showed strong EGFR inhibitory activity compared to Erlotinib (0.439?nM) and these results are in agreement with the docking study. These results suggest that compounds could probably be promising anticancer agents with EGFR inhibitory activity.     

Phosphine oxide-functionalized polyfluorene derivatives:Synthesis,photophysics,electrochemical properties,and electroluminescence performance

A series of phosphine oxide-functionalized polyfluorene derivatives,PFH-PO-40-1 (P1),PFH-PO-20-1 (P2),PFH-PO-10-1 (P3),and PFH-PO-1-1 (P4),were prepared via a palladium-mediated Suzuki cross-coupling reaction.The structures and purities of all polymers were fully characterized by 1H and 13C NMR,UV-vis and photoluminescent spectroscopy,gel permeation chromatography,and TGA/DSC.Their emission features showed single broad peaks at about 445 nm in film,compared with those in dilute solutions,which might be caus...     

二苯胺取代吖啶衍生物发光材料的合成、表征及电致发光性能

设计合成了2个苯胺取代吖啶衍生物N3,N3,N6,N6-四苯基吖啶基-3,6-二胺(1)和N3,N3,N6,N6-四对甲苯基吖啶基-3,6-二胺(2),通过化学修饰在吖啶核的两端引入二苯胺取代基可以调节化合物的能级和堆积结构等性质,从而使这些吖啶衍生物具有良好的发光性能,可用于制备电致发光器件.基于吖啶衍生物为掺杂发光材料制备的电致发光器件均呈现绿光发射,器件开启电压较低(2.4 V),以化合物1和2制备的器件最高功率效率分别为4.9和8.2 lm/W.考察了其光物理、电化学、热学和荧光量子效率等性能.结果表明,化合物1和2具有较高的量子效率及匹配的能级结构,这是获得较高电致发光效率的基础.     

Theoretical investigations on electronic structures and photophysical properties of N-heteroaryl carbazole derivatives as host materials

The carbazole-endcapped host molecules with tailoring different heteroaryl core and meta-position linkage mode have great potential on phosphorescent organic light-emitting diodes. To provide a profound view on structure?Cproperty relationships, new linear-shaped counterparts have been designed based on the existing molecular composition and the linkage at para-position (p-type molecules). A series of studies about the influence of the linkage mode on optical and electronic properties of these carbazole derivatives have carried out via density functional theory and time-dependent density functional theory calculations. The geometric and the electronic structure of these molecules in the ground states, ions states, and lowest triplet states have been calculated especially focusing on the analysis of highest occupied molecular orbitals, lowest unoccupied molecular orbitals, energy gaps, triplet energies, ionization potentials, electron affinities, reorganization energies, triplet exciton-formation fraction, and absorption spectra. These optoelectronic properties can be effectively tuned by the chemical modifications of different linkage pattern. The good coordination between our calculated results and the available experimental data has been observed. The study reveals that the designed p-type molecules show great promise as new high-performance red host materials with large triplet energy, narrow energy gap, good electron and hole-transport properties, and high triplet exciton-formation fraction.     

Influence of the composition of compositions based on organic compounds and chelate complexes of aluminun and yridium on their electroluminescent properties

The effect of the composition of electroluminescent compositions based on PEDOT, TPD, Alq₃, and Ir(PPy)₃, the structure of the cathode (Al, CaMg/Ag, Al/Ag), and the possibility of forming of emitting layers (thermovacuum deposition and centrifugation) on their current-voltage, voltage-brightness, and spectral characteristics has been studied. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 1, pp. 54–58, January–February, 2009.     

Synthesis and properties of terthiophene and bithiophene derivatives functionalized by BF2 chelation: a new type of electron acceptor based on quadrupolar structures

Terthiophene and bithiophene derivatives functionalized by BF(2) chelation were synthesized as a new type of electron acceptor, and their properties were compared to those of bifuran and biphenyl derivatives. These new compounds are characterized by quadrupolar structures due to resonance contributors generated by BF(2) chelation. The bithiophene derivative has a strong quadrupolar character compared with the bifuran and biphenyl derivatives because their hydrolytic analyses indicated that the bithiophene moiety has a larger on-site Coulomb repulsion than the others. The terthiophene derivative has a smaller on-site Coulomb repulsion than the bithiophene derivative due to the addition of a thiophene spacer. These BF(2) complexes exhibit long-wavelength absorptions and according to measurements of ionization potentials and absorption edges they have energetically low-lying HOMOs and LUMOs. The crystal structure of the bithiophene derivative is of the herringbone type, with short F···S and F···C contacts affording dense crystal packing. n-Type semiconducting behaviour was observed in organic field-effect transistors based on these BF(2) complexes.     

Silver(I), nickel(II) N-heterocyclic carbene complexes based on bidentate bis-imidazolium salt with a quinoxaline linker: syntheses,structures, and characterization

Quinoxaline-bridged bidentate bis-imidazolium dicarbene ligand 1,1′-(quinoxaline-2,3-diyl)bis(3-methyl-1H-imidazol-3-ium) hexafluorophosphate salt H₂L·2PF₆ (3) was prepared by a two-step reaction based on 2,3-bis(imidazol-1-yl)quinoxaline (1). First, the 2,3-bis(imidazol-1-yl)quinoxaline reacted with CH₃I resulting in the 1,1′-(quinoxaline-2,3-diyl)bis(3-methyl-1H-imidazol-3-ium) iodide salt H₂L·2I (2), then through anion exchange reactions with NH₄PF₆ in water produced the desired bis-imidazolium bidentate ligand H₂L·2PF₆ (3). Reaction of the bidentate bis-imidazolium ligands H₂L·2PF₆ (3) with Ag₂O in acetonitrile gave the macrocyclic binuclear silver(I) carbene complex [Ag₂(L)₂]·2PF₆·CH₃CN (4). Nickel carbene complex [Ni(L)PPh₃Cl]·PF₆·2DMSO (5) was obtained via transmetalation of 4 with Ni(PPh₃)₂Cl₂ in DMSO. The bidentate carbene ligand is a chelating ligand in 5, while bridging in 4. The imidazolium ligand H₂L·2PF₆ (3) and transition metal carbene complexes 4 and 5 have been fully characterized by elemental analysis, NMR, ESI-MS spectroscopy, and X-ray diffraction analyses. Furthermore, the UV and luminescent properties of 3–5 were also studied.