新型噁二唑有机电致发光小分子光电性质研究

通过升降温差热分析(DSC)曲线、偏光显微镜、紫外吸收光谱、电化学行为曲线以及多层器件等,研究了噁二唑衍生物小分子的电学和光学性质,发现其同时具有液晶性、电子和空穴传输性、发光性等优良性能.引进R-OXD(En)层后的多层器件在低于3 V时就能得到可见光发射,在7 V时可以得到光亮度为1000 cdm^-2.此系列小分子可降低有机电致发光器件开启电压,提高发光亮度和发光效率,是一种非常具有吸引力的有机电致发光小分子.     

双光子吸收材料二苯乙烯衍生物的合成及光谱性质

设计、合成并用红外光谱、1H NMR、元素分析表征了三种用于双光子吸收材料的二苯乙烯衍生物,4,4′-双(二苯氨基-反式-苯乙烯基)联苯(BPSBP),4,4′-双(二乙氨基-反式-苯乙烯基)联苯(BESBP)和4,4′-双(9-咔唑基-反式-苯乙烯基)联苯(BCSBP)。实验结果表明三者最强的单光子吸收出现在350～400 nm之间,且单光子吸收和荧光光谱中表现出明显的溶剂化显色效应,揭示了分子内对称电荷转移的本质,双光子荧光光谱则揭示了单光子和双光子吸收具有相同的发射机理。利用双光子上转换荧光法测试发现,三种双光子吸收材料在800 nm飞秒激光的激发下具有较大的吸收截面,分别为892,617和483 GM,这表明在双光子领域有潜在的应用价值。     

Synthesis of Quinolone Substituted Pyrazoles,Isoxazoles and Pyridines as a Potential Blue Luminophors

Series of quinolone C₃-substituted pyrazolines, isoxazolines, pyridines and pyrimidines were synthesized in good yields by the cyclocondensation reactions of 1, 2-unsaturated ketones and hydrazines, hydroxylamine hydrochloride and dimedone respectively. The quinolone derivatives (3, 5 and 7) were synthesized and further studied for their photophysical properties. High absorption and quantum yield are found for N₁-phenyl and C_3,4-dimethoxy substituents on phenyl ring (3h). Energy optimization by PM6 methods showed high stability required for selection of suitable candidates to be use as future blue emitters.     

Synthesis,X-Ray Crystal Structures and Optical Properties of Novel Substituted Pyrazoly 1,3,4-Oxadiazole Derivatives

Novel pyrazoly 1,3,4-oxadiazole derivatives were synthesized and characterized by ¹H NMR, IR, HRMS and X-ray diffraction analysis. UV–vis absorption and fluorescence properties of these compounds in different solutions showed that the maximum absorption wavelength was not significantly changed in different solvents; however, maximal emission wavelength was red-shifted with the increase of solvent polarity. Absorption λ_max and emission λ_max was less correlated with substituent groups on aryl rings.     

新型螺芴类蓝光材料的合成与性能

通过一系列反应成功合成了一种新型螺芴化合物DCSF,通过核磁共振氢谱(¹H NMR)、核磁共振碳谱(¹³C NMR)、质谱(MS)、傅立叶-红外(FT-IR)光谱对其结构进行表征,利用紫外可见吸收光谱、荧光光谱研究其发光性能。以硫酸奎宁的0.05 mol/L的硫酸溶液为标准,测定其荧光量子产率为0.391。通过循环伏安曲线,计算出DCSF的HOMO和LUMO能级的能隙E_g为3.20 eV。     

菲并咪唑衍生物蓝光材料的合成、光物理性质及理论计算

合成了两个蓝光材料2-苯基-1H-[9,10-d]菲并咪唑(Phen-PI)和2-吡啶-1H-[9,10-d]菲并咪唑(PyriPI),光物理分析表明Phen-PI和Pyri-PI的最大发射峰分别位于371.5 nm,388.5 nm和403.5 nm,相对量子效率分别为0.383和0.528,激发态衰减寿命分别为3.87 ns和3.68 ns。通过密度泛函理论(DFT)对化合物的前线分子轨道成分和能级分布分析表明,当把Phen-PI中的苯基被吡啶环取代后,Pyri-PI的HOMO能级和LUMO能级分别下降0.09 e V和0.23 e V,同时Pyri-PI的HOMO轨道和LUMO轨道的能级差比Phen-PI减少0.14 e V,在理论层面上解释了Pyri-PI发射光谱的红移。     

新型含噁二唑环双元席夫碱的合成与光谱特性

4-硝基苯甲酸与硫酸联氨在H₃PO₄/P₂O₅作用下脱水环化生成2, 5-二(4-硝基苯基)-1,3, 4-噁二唑(1),(1)被Zn/CaCl₂还原为2, 5-二(4-氨基苯基)1,3, 4-噁二唑(2),(2)与芳香醛反应合成8个含噁二唑环的新型双元席夫碱,产率为65%～81%,用1H NMR,FTIR,MS对其结构进行了验证。研究了它们的UV-Vis光谱和荧光光谱,并用循环伏安法测定了其电化学性能。UV-Vis光谱表明：标题化合物没出现噁二唑环和席夫碱单元所对应的特征吸收峰,共轭效应使两个结构的能带发生了部分杂化而形成新的能带结构,在345～357 nm出现最大吸收峰。荧光光谱表明：目标化合物发射强的紫蓝色荧光,在390～407 nm出现最大发射峰。电化学性能表明：电子亲合势为2.36～3.04 eV,离子势为5.35～6.06 eV,除了3a,3h外,它们的电子传输性比常用的电子传输材料PBD(E_A=2.82 eV)优越。此研究为进一步研究其在有机电致发光器件中的应用提供了参考。     

Synthesis and Optoelectronic Properties of Symmetrical Thiophene Based 2,5-disubstiuted 1,3,4-oxadiazoles: Highly Fluorescent Materials for OLED Applications

Symmetrical 2,5-disubstituted thiophene derivatives containing 1,3,4-oxadiazole moiety bearing different aromatic substitutions were synthesized by employing convenient and simple synthetic protocols using thiophene-2,5,dicarboxylic acid as a starting material. The structures of these target molecules were established by their analytical and spectral data. The photophysical and electrochemical studies were carried out on these compounds and found that they exhibit good fluorescent properties with high quantum yield.     

有机合成——光电子材料研究的重要工具

以有机电致发光显示与照明技术、有机太阳能电池等为代表的有机光电子器件在世界范围内吸引了产业界和研究机构的关注。新型有机光电材料的开发是近些年来有机光电子飞速发展的基石和巨大推动力。合成方法与材料设计思路的突破,使包括小分子和聚合物光电材料的性能得到了飞跃式发展。从材料的设计与合成入手,综述了材料化学结构与分子自组织行为及最终器件性能的关系。以窄带共轭聚合物、全共轭嵌段聚合物、超支化材料等为例阐述了上述材料溶液与本体中的自组织行为,以及用于有机太阳能电池给体材料时形貌对器件行为的影响。     

Synthesis and Properties of Diphenylcarbazole Triphenylethylene Derivatives with Aggregation-Induced Emission, Blue Light Emission and High Thermal Stability

New aggregation-induced emission materials derived from diphenylcarbazole triphenylethylene were prepared. The thermal, photophysical, electrochemical and aggregation-induced emissive properties were investigated. All the compounds had strong blue light emission capability and excellent thermal stability. Their maximum fluorescence emission wavelengths were between 450 to 460 nm in TLC plates, while their glass transition temperatures ranged from 162.2 to 182.4 °C. The decomposition temperatures of the synthesized compounds were all well over 500 °C. The synthesized compounds possessed aggregation-induced emission (AIE) properties, which exhibited enhanced fluorescence emissions in aggregation states or in solid states. The HOMO energy levels estimated from the oxidation potentials were found in the range from 5.49 to5.52 eV. The lowest unoccupied molecular orbital/highest occupied molecular orbital (LUMO/HOMO) energy gaps (ΔEg) for the compounds were estimated from the onset absorption wavelengths of UV absorption spectra and ranged from 3.04 to 3.20 eV.     

基于四苯乙烯基的水杨醛缩芳胺希夫碱化合物的合成及性能研究

将四苯乙烯基与取代水杨醛通过碳氮双键连接起来,合成了基于四苯乙烯基的水杨醛缩芳胺希夫碱TPE-SA1、TPE-SA2、TPE-SA3、TPE-SA4、TPE-SA5。利用IR、NMR、MS和元素分析等对其分子结构进行表征,通过紫外-可见光谱、分子荧光光谱、循环伏安分析法和热重测试分别考察了该类化合物的光学、电化学和热稳定性质。实验结果表明:该类化合物在纯THF溶液中,分别在260 nm和370 nm左右处出现B带和R带紫外吸收峰;在四氢呋喃/水的混合溶液中,表现出典型的聚集诱导发光(AIE)性能。目标化合物的热分解温度分别为262,283,295,278,299℃,具有较好的热稳定性。它们的电离势分别为5.31,5.43,5.41,5.30,5.15eV,电子亲合势均大于4.3 eV。     

Synthesis, Characterization, Optical Properties and Theoretical Studies of Novel Substituted Imidazo[1,5-a]pyridinyl 1,3,4-Oxadiazole Derivatives

Novel imidazo[1,5-a]pyridinyl 1,3,4-Oxadiazole derivatives were synthesized and characterised by IR, ¹H NMR and HRMS.UV-vis absorption and fluorescence properties of these compounds in different solutions showed that the maximal emission wavelength was not significantly changed in different solvents; however, maximum absorption wavelength was blue-shifted with the increase of solvent polarity. Absorption λ_max and emission λ_max was less correlated with substituent groups on benzene rings. The calculated molecular orbital correlates well with their absorption.     

Design,Synthesis, Photophysical Properties,Biological Estimation and Molecular Docking Studies of Novel Schiff Base Derivatives as Potential Urease Inhibitors

A quinoline functionalized two novel fluorescent Schiff bases, N-(quinolin-2-ylmethylene) anthracen-1-amine (SB1) and 2-(quinolin-2-ylmethyleneamino) benzene thiol (SB2) were synthesized and confirmed by using ¹H NMR, IR and GC-MS techniques. The spectroscopic properties were examined by absorption spectroscopy and fluorescence spectroscopy. The absorption and fluorescence spectra of the probes (SB1 and SB2) were measured in a variety of solvents. Both the compounds were tested for urease inhibitory activity. The synthesized compound SB2 proved to be the most effective screening for enzyme inhibitory activity with IC₅₀?=?0.111 μM than SB1 (IC₅₀?=?0.287 μM). Molecular docking studies were performed to delineate the binding affinity and conformational positions of chemical compounds within the active region of the target protein. In-vitro analysis depicts the potency of SB1 in free radical scavenging as compared to the reference drug vitamin C.     

Fluorescent Triphenyl Substituted Maleimide Derivatives: Synthesis,Spectroscopy and Quantum Chemical Calculations

In this paper we describe a semi-empirical quantum method for predicting the wavelength of maximum fluorescence excitation and emission for several known and new maleimide derivatives. All new maleimides, containing a N-Benzyl attachment, were successfully synthesised via a tandem Suzuki reaction with aryl boronic acids containing either an electron donating, electron withdrawing functional groups. Absorption and emission spectra calculated using the semi-empirical AM1 method with excited state ZINDO calculations proved more reliable than either Hartree-Fock Configuration interaction or time dependent density functional methods. Calculated absorption and emission wavelengths were compared with 26 experimental spectra from known or newly synthesised maleimides and found to have provide reasonable predictions, with an average deviation of less the 6% for absorption maxima and less than 4% for emission peaks. The described method provides a strong benchmark for the accuracy that can be expected from theoretical predictions of fluorescence spectra.     

新型高分子蓝色荧光材料的制备及性能

以吡唑啉为发光功能基团,设计并合成了4种新的聚酰胺类高分子化合物,采用核磁共振氢谱(H 1NMR)和凝胶色谱(GPC)对其结构进行了确证。进而测定了高分子化合物的液体及固体荧光激发、发射光谱,高分子J1,J2和J3具有良好的液体及固体荧光发光能力。所制备的高分子材料具有良好的成膜能力、成本低廉、热稳定性好,有望在电致发光器件中广泛应用。     

新型3,4-二烷基取代聚噻吩的合成、光学及电化学性能

通过Heck偶联法制备了一种新型聚噻吩衍生物——2,5-二乙烯基-3,4-二辛基噻吩-共-2,5-二苯基-1,3,4-(口恶)二唑(PO2TV-OXD),用核磁共振氢谱(1H NMR)及凝胶色谱(GPC)对其结构进行分析和表征.用紫外-可见光谱(UV-Vis)、荧光光谱(PL)及电化学分析研究其光学和电化学性能,并与3,4-二辛基噻吩均聚物(PO2T)进行了对比研究.研究表明:主链上引入吸电子能力较强的1,3,4-(口恶)二唑基团,明显增加了聚合物的能隙,提高了聚合物的荧光量子效率.     

两种新型芴衍生物的合成、晶体结构及光谱性能

合成了两种新型芴衍生物:2,7-二(3,5-二(三氟甲基)苯基)-9,9-二乙基芴(1)和2,7-二(4-氟苯基)-9,9-二乙基芴(2)。通过元素分析、红外光谱(IR)、核磁共振氢谱(1H NMR)以及单晶X射线衍射对其结构进行了表征。化合物1属于单斜晶系,P21/c空间群;化合物2属于三斜晶系,P-1空间群。通过紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明:在CH2Cl2溶液和固态薄膜中,化合物1、2在350~400 nm波段有吸收峰,归属于π-π*电荷跃迁;化合物1、2的光学带隙E g分别为3.31 eV和3.30 eV,并且均有强烈的蓝色荧光发射现象(激发波长为330 nm),在二氯甲烷中的荧光量子效率分别为0.62和0.61,固态荧光寿命分别为6.39 ns和9.00 ns。     

新型双噻吩衍生物的合成、晶体结构及光谱性能

通过Suzuki偶联反应,用不同基团对双噻吩原料上的溴原子进行取代后合成了一系列双噻吩衍生物:3-(5′-溴-[2,2-双噻吩]-5-基)吡啶(Dt-1)、5,5-双(吡啶-3-基)-2,2-双噻吩(Dt-2)、5-(3,5-双(三氟甲基)苯基)-2,2-双噻吩(Dt-3)、5,5-双(3,4,5-三氟苯基)-2,2-双噻吩(Dt-4)。通过红外光谱(IR)、质谱(MS)、核磁共振氢谱(¹H NMR)及单晶X射线衍射对其结构进行了表征。通过紫外-可见吸收光谱和荧光光谱研究了其发光性能。结果表明,在CH₂Cl₂溶液中,化合物Dt-1在349 nm激发光作用下在390～470 nm区域有较强的双荧光发射行为,两个最大发射峰分别为403 nm和422 nm;化合物Dt-2在372 nm激发光作用下在400～480 nm区域即紫色和蓝色光区有较强的双荧光发射行为,最大发射峰分别为430 nm和440 nm;化合物Dt-3在349 nm激发光作用下在418 nm处有最强的荧光发射;化合物Dt-4在371 nm激发光作用下于436 ...