1，1-二（苯并咪唑-2-基）-2-（N-乙基咔唑-3-基）乙烯的合成及其性能研究

以六氢吡啶为催化剂,通过Vilsmerier-Haack和Knoevenagel反应合成了一种新型的芳稠杂环化合物1,1-二（苯并咪唑-2-基）-2-（N-乙基咔唑-3-基）乙烯,产率为72.53%。利用元素分析、FT-IR、UV-Vis、¹H NMR、溶液和固体荧光光谱、循环伏安（CV）分析、TG-DTA热分析研究了产物的结构、光学特性、电化学特性和热稳定性。该化合物在DMF、DMSO和DCM 3种溶剂的稀溶液中均具有290 nm和375 nm两处紫外吸收峰以及470 nm处的蓝绿色荧光发射。不同DMSO和DCM体积比的混合溶剂的溶液荧光表明,该化合物具有明显的AIE荧光效应。固体荧光光谱表明,产物在327 nm和436 nm有两处激发峰,最大发射峰位于484 nm,相 比于溶液荧光发生了红移现象。由循环伏安测试结果计算获得产物的能隙为2.79 eV,电离势为5.43 eV,电子亲和势为2.85 eV,表明产物具有良好的电子传输能力。TG/DTA测试结果显示目标产物具有良好的热稳定性。     

一种苯磺酰基/螺-9,9′-氧杂蒽芴双极性分子的简易合成法:分子结构与光电性质

利用一种简易合成法制备了2′-苯磺酰基-螺-9,9′-氧杂蒽芴(PSSFX)。热重分析曲线和差热扫描曲线表明该化合物在222℃时失重5%,加热到160℃没有玻璃化转变温度,其熔点为124℃。通过磷光光谱计算得到该化合物的三线态能级T_1为2.77 eV。利用密度泛函计算得知其HOMO(-5.83 eV)和LUMO(-1.62 eV)轨道相分离。通过循环伏安法得到其HOMO、LUMO和E_g分别为-6.33,-2.34, 3.94 eV。这表明缺电子的苯磺酰基有利于改善其电子注入/传输性能。PSSFX在二氯甲烷溶液和晶体粉末的紫外吸收峰分别位于267 nm和274/351 nm左右,发射峰分别位于408 nm和341 nm左右。     

在双波长下识别Fe3+的一种新型可视化荧光探针的合成及性能

合成了一种新型四苯乙烯-罗丹明化合物L,通过紫外-可见吸收光谱、分子荧光光谱、裸眼和循环伏安分析法等分别研究了化合物L的聚集诱导发光性能、对金属阳离子的识别性能和电化学性能。实验结果显示:化合物L在乙醇-水的混合溶剂中表现出典型的聚集诱导发光性能;L在EtOH/H_2O(V∶V,1∶1,Tris-HCl,pH=7.0)溶液中随Fe~(3+)的加入,化合物L的EtOH/H_2O(V∶V,1∶1,Tris-HCl,pH=7.0)溶液显示出明显的颜色变化,由无色变成红色,除Al~(3+)、Cr~(3+)略微变红外,其他金属离子无明显变化,这表明化合物L可作为裸眼识别Fe~(3+)的探针;当选用激发波长350 nm时,在508 nm处的荧光发射强度发生猝灭,猝灭比为87.5%,检出限为4.56×10~(-6) mol/L;激发波长为530 nm时,在582 nm处荧光发射强度呈增大趋势,较加入前增大了49.6倍,检出限可达7.4×10~(-7) mol/L。由此可见,L在用不同激发波长激发时,在两个不同荧光发射波长下分别实现了对Fe~(3+)的"turn-off"和"turn-on"识别,因此L可作为一种具有高灵敏性和专一选择性的可视化Fe~(3+)荧光探针。并经Job's曲线、紫外和荧光滴定、核磁滴定、扫描电镜初步确定了探针L和Fe~(3+)的络合机理,探针L和Fe~(3+)的络合比为2∶1,整个测试在中性条件下进行,使得该类探针在生物体系或环境中有潜在的应用价值。且它的电离势为5.77 eV,电离势与正电极的功函数(5.5 eV)较匹配,有望开发成为空穴传输材料。电子亲合势为3.71 eV,比常见的电子传输材料PBD(E_A=2.82 eV)的电子亲和能大,有望开发为电子传输材料,所合成的化合物也可作为一类具有潜在应用价值的光电材料。     

一种锌希夫碱配合物的表征及发光性能研究

合成并通过真空升华提纯得到了一种高纯度的希夫碱有机金属配合物水杨醛缩邻苯二胺合锌。通过元素分析、红外光谱、热重-差热曲线、紫外-可见光吸收光谱、荧光发射光谱和光致发光光谱表征了其结构、热稳定性以及能带结构。实验结果表明：水杨醛缩邻苯二胺合锌的玻璃化温度(T_g)高达183 ℃,分解温度为449 ℃; 水杨醛缩邻苯二胺合锌是一种多晶粉末状的发光材料,在紫外光的激发下,在四氢呋喃溶液体系中的荧光发射峰在508 nm处,为蓝绿色荧光,色纯度高,荧光量子效率高,禁带宽度2.62 eV; 利用真空热蒸镀很容易制备高质量薄膜,其发射峰在562 nm处,半高宽为48.5 nm的黄绿光发射。利用水杨醛缩邻苯二胺合锌为发光层制备了黄光有机电致发光器件。     

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。     

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。     

一种新型希夫碱锌配合物的合成及光谱学性质

合成了一种希夫碱有机金属配合物2-羟基-1-萘甲醛缩邻苯二胺合锌(ZnL)。通过质谱、元素分析、红外光谱、热重分析对其结构进行了表征;利用紫外-可见光吸收光谱、激发和发射光谱研究了该配合物的光物理性能。结果表明:ZnL的热分解温度为433.2℃,具有很好的热稳定性;在DMF溶液体系中,配合物ZnL的紫外吸收带位于250~500 nm,荧光激发带位于343~493 nm,在紫外光的激发下发射峰在626 nm处,为橙红色光,最佳激发波长为470 nm,禁带宽度2.32 eV。     

六硝基菧的紫外光解

采用紫外-可见光谱、X-射线光电子能谱、电子自旋共振谱及质谱等实验手段研究了固态含能材料六硝基菧（HNS）在365 nm紫外光照下的光解机理。HNS的乙腈溶液被紫外光照射后,在310 nm和350 nm处出现了两个新的吸收峰。X-射线光电子能谱实验中,N元素和O元素的窄谱图分别在401 eV和528 eV处出现了新峰。质谱分析则显示在质荷比403和329处出现了两个新的特征离子峰。实验结果表明:CNO2键断裂、分子中NO2基团异构化为亚硝基,以及随后的NO消去等过程均可能发生在六硝基菧的紫外光解反应过程中。     

光致变色化合物水杨醛缩对硝基苯胺的合成及发光

在无水乙醇溶液中,用苯胺、对硝基苯胺分别与水杨醛反应合成了两种席夫碱化合物水杨醛缩苯胺、水杨醛缩对硝基苯胺,通过元素分析、红外光谱的表征确定了产物的分子结构。研究了水杨醛缩苯胺和水杨醛缩对硝基苯胺的荧光性质,结果表明,两个化合物在甲醇、无水乙醇、丙酮、DM F溶液中能够发射荧光。水杨醛缩苯胺在所有溶液中、水杨醛缩对硝基苯胺在丙酮、DM F溶液中的发光机理均为π＊→n发光。水杨醛缩对硝基苯胺在甲醇、无水乙醇溶液中具有良好的光致变色性能,其变色过程是由烯醇式结构向酮式结构转变,阐明了基于分子内的质子转移的光致变色机理。     

一种新的有机光致变色及热致变色化合物间氨基苯甲酸缩3,5二氯水杨醛希夫碱

制备了间氨基苯甲酸缩3,5-二氯水杨醛希夫碱,利用红外(IR)、核磁(¹H NMR)、质谱(MS)和元素分析对化合物结构进行了表征。研究了它的荧光性质和热稳定性。对化合物的紫外可见(UV-Vis)光谱和荧光光谱的研究表明,该化合物在DMF溶液中具有较好的光致变色和热致变色性能。化合物的吸光度值和最大发射波长与时间或温度呈线性关系,进一步说明该化合物是性能良好的光致变色及热致变色材料。     

Studies of Luminescence Performance on Carbazole Donor and Quinoline Acceptor Based Conjugated Polymer

We report on the synthesis of conjugated polymer (CV-QP) containing carbazole (donor) and quinoline (acceptor) using Wittig methodology. The structural, optical and thermal properties of the polymer were investigated by FT-IR, NMR, GPC, UV, PL, cyclic voltammetry, atomic force microscopy (AFM) and thermogravimetric analysis (TGA). The polymer exhibits thermal stability upto 200 °C and shows good solubility in common organic solvents. The polymer has optical absorption band in a thin film at 360 nm and emission band formed at 473 nm. The optical energy band gap was found to be 2.69 eV as calculated from the onset absorption edge. Fluorescence quenching of the polymer CV-QP was found by using DMA (electron donor) and DMTP (electron acceptor). AFM image indicated that triangular shaped particles were observed and the particle size was found as 1.1 μm. The electrochemical studies of CV-QP reveal that, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the CV-QP are 6.35 and 3.70 eV, which indicated that the polymers are expected to provide charge transporting properties for the development of polymer light-emitting diodes (PLEDs).     

含吡啶环的双醛腙类试剂的合成及其光谱研究

有机电致发光技术在彩色大屏幕平板显示技术方面己经显示出了广阔的应用前景,是当今国际平板显示技术领域研究的热点之一。开发性能优良的电子传输材料是提高有机及聚合物 LED 性能的关键。双席夫碱类金属配合物同时满足了电荷平衡和配位数饱和两个条件,可以得到非常纯的荧光,能够成为良好的电致发光材料。文章设计并合成了四种新的含吡啶环的双醛腙类化合物,通过红外光谱、元素分析、荧光光谱对合成的化合物进行了表征,确定了化合物结构。对所合成化合物红外光谱进行了分析,确定了该类化合物的红外特征吸收峰;荧光光谱表明该类化合物具有良好的荧光性,其最大发射波长在420～440 nm之间,其荧光强度的大小与衍生物中不同的取代基有关,—OH、呋喃环、胡椒醛等起供电子作用的基团,使荧光波长发生红移。     

热稳定空穴传输材料的合成及其电致发光器件

合成了两种NPB的新衍生物:N,N’-二(1-萘基)-N,N’-二(4-甲基苯基)-1,1’-联苯-4,4’二胺(NTB)和N,N’-二(1-萘基)-N,N’-二(4-叔丁基苯基)-1,1’-联苯-4,4’二胺(NBB)。DSC测得其玻璃态转变温度分别为108℃和129℃,表现出好的热稳定性。紫外光电子能谱测得其电离势均为5.2eV。NTB和NBB固体光致发光光谱的最大发射波长分别位于455nm和460nm。分别以NPB、NTB、NBB作为空穴传输层材料(HTM)制作了结构相同的有机电致发光器件,3种器件发光光谱相同,均为Alq₃的绿色发光,器件的起亮电压分别为11,9,8V,在15V工作电压时的亮度分别为1000,1300,1200cd/m²,初步研究了器件的发光特性和稳定性。     

Electrochemical synthesis and characterization of a new conducting polymer: Polyrhodanine

An antimicrobial drug, rhodanine (Rh), was electrochemically polymerized on a Pt electrode using cyclic voltammetry (CV). The high quality and homogeneous polyrhodanine (pRh) films with a dark-purple color were obtained. The chemical structure characterization was investigated by Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy techniques. Further, thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques used to investigate thermal properties of the film. It is found that thermal stability of pRh films is relatively high. It is also observed that tetrahydrofurane (THF) and N-methyl-2-pyrrolidone (NMP) are good solvents for the polymer.     

Synthesis and characterization of highly fluorescent europium functionalized β-diketonate complexes

Several functionalized β-diketones and their europium complexes have been synthesized and characterized. The UV-Vis absorption, photoluminescent spectra, thermal and electrochemical properties of these complexes were investigated. The thermal analysis shows that the complexes have good thermal stability. By introducing the number of extended phenyl rings we succeeded in obtaining europium complexes with extremely high photoluminescent quantum yield (PLQY) in solution due to strong site isolation effect.     

Electrochemical,thermal,and photophysical properties of novel two-photon absorption chromophores

Electrochemical, thermal, and photophysical properties of novel two- （BPODPA）, four- （BBPOPA）, and six-branch （TBPOA） triphenylamine chromophores are studied. The decomposition temperature of chro- mophores reaches 373 - 412 ℃. The electrochemical properties is explored by cyclic voltammetry. The ionization potential of chromophores is in the range of 5.14 - 5.18 eV. Excitation at 400 nm reveals emission peaks at 483 - 487 nm and the fluorescence quantum yields are 0.73 - 0.75 in CH2Cl2. Two-photon absorption （TPA） properties of chromophores are measured by nonlinear transmission method. The maximum TPA cross-section values are measured at 758 nm to be 20369 GM （1 GM=10^-50 cm^4 -s/photon） for TBPOA, 7024 GM for BBPOPA, and 1227 GM for BPODPA, respectively. When pumped with 800-nm laser irradiation, chromophores show strong two-photon excited blue-green fluorescence at 502 - 518 nm. These results provide a basis for understanding the electronic and optical properties of the conjugated multi-branch chromoohore in terms of the underlying molecular and electronic structures.     

New counter electrode prepared as vanadium oxide and V/Ce oxide films: preparation and characterization

Vanadium oxide and mixed V/Ce-oxide films at 78, 55, 38, 32 atomic % of V were prepared via the sol-gel route from an aqueous colloidal solution of inorganic precursors. The influence of the added cerium precursor on their electrochemical, optical and structural properties was investigated by cyclic voltammetry (CV), X-ray analysis, IR spectroscopy and UV-VIS techniques. The electrochemical stability of films was tested by CV measurements in 1 M LiClO₄ in propylene carbonate electrolyte. The addition of CeO₂ improved the poor stability of vanadium oxide films and enhanced their ion-charge capacity up to 30 mC/cm² for thicknesses about 300 nm. The intercalation of Li⁺ ions in vanadium oxide and V/Ce-oxide films was followed by FT-IR spectroscopy performed at near-grazing incidence angle (NGIA) conditions in combination with CV measurements at potentials of −1.5 V and +2.0 V (vs. Ag/AgCl). The observed shift of V–O_v vibrations in the IR spectra confirmed the intercalation of Li⁺ ions.     

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.