溶剂效应和取代基效应对2-(2-氨基苯基)苯并噻唑光谱性质及激发态分子内质子转移的影响

合成了多种2-(2-氨基苯基)苯并噻唑(APBT)氨基氢原子被供电子及吸电子基团取代的衍生物, 并用紫外光谱﹑荧光光谱等方法和密度泛函理论(DFT)计算研究了溶剂效应和取代基效应对衍生物的光谱性质及激发态分子内质子转移(ESIPT)的影响规律. 结果表明, 相比于非极性溶剂环己烷, 随溶剂极性的增加及APBT-溶剂分子间氢键的形成, APBT的紫外-可见最大吸收峰和荧光最大发射峰均发生了一定程度的红移, 并对APBT的ESIPT产生了影响. 在APBT分子的氨基氮原子上引入不同的吸电子或斥电子取代基, 对氮原子的电荷性质有较大的影响. 在环己烷溶剂中, 甲基取代后的APBT仅有单重荧光发射峰, 体系未发生ESIPT过程; 而COCH₂Cl等吸电子基团能促进APBT的ESIPT, 其荧光发射光谱出现了明显的双重峰, 表明体系发生了激发态分子内质子转移反应. 量子化学的理论计算较好地验证了光谱实验结果.     

苯并噻唑螺萘并吡喃类化合物的微波合成与性质

苯并噻唑螺萘并吡喃类化合物的微波合成与性质;微波辐射法;溶剂效应;荧光效应     

1,4—双（取代苯乙炔基）苯电子光谱的溶剂效应

1,4-双(取代苯乙炔基)苯是较好的荧光物质并有良好的激光转换效率。本文测定了1,4-双(苯乙炔基)苯1和1,4-双[(4-叔丁基苯基)乙炔基]苯2在14种溶剂中的紫外吸收光谱和荧光发射光谱,并用多元回归QSAR程序研究了它们的溶剂效应。 1 实验 UV谱用Beckman DU-8B紫外可见分光光度计测定。荧光光谱在MPF-4荧光仪上测得。     

两个新的苯并噻唑衍生物的合成与光物理性质

以苯并噻唑、苯乙酰基和吡啶阳离子为电子受体,二乙烯基苯为共轭桥,合成了两个新的A-π-A′型苯并噻唑衍生物:4-(2-苯并噻唑)-乙烯基查尔酮(1)和4-{4-[2-(苯并噻唑)乙烯基]苯乙烯基}-N-甲基吡啶碘盐(2).研究了它们在溶液和固体基质中的光物理性质.研究发现:染料2由于具有较强的极性和较好的平面性,从而具有较长的吸收、发射峰和较强的荧光发射.有机染料在聚甲基丙烯酸甲酯/溶胶-凝胶复合玻璃中的发光行为与聚甲基丙烯酸甲酯和溶胶-凝胶玻璃二者的基质性质有关,同时由于固体基质中分子发生聚集的可能性降低,荧光强度相对于同浓度溶液增强,稳定性提高.     

三苯胺衍生物光物理性质的研究

研究了4-醛基-三苯胺(kTA)和4,4′-二醛基-三苯胺(BTA)的光谱性质。由于这两种化合物的共轭体系中既有电子给体(胺基)又有电子受体(醛基),它们在激发态发生分子内扭曲的电荷转移(TICT)。通过对FTA和BTA的荧光发射的溶剂效应、温度效应、粘度效应以及低温77K荧光的研究,发现FTA和BTA在极性溶剂中的荧光发射谱带中包含了光诱导电荷转移(ICT)和TICT(A带)2个组分,而在非极性溶剂中只有ICT带(B带),并讨论环境对TICT态的影响。另外,荧光猝灭方法也证实了这一点。     

新型pH敏感吡喃腈衍生物的合成及其荧光性能

以2,6-二甲基-4H-吡喃-4-酮、丙二腈和4-(4-甲酰苯基)吗啉为原料,合成了2种含吡喃腈(DCM)结构的化合物:2-甲基-6-(4-吗啡啉苯乙烯基)-4-二氰甲烯基吡喃(MDCM)和2,6-二(4-吗啡啉苯乙烯基)-4-二氰甲烯基吡喃(BDCM)。通过1H NMR、元素分析等确定了其结构,并探讨了所得化合物的荧光性能,研究了化合物在不同浓度下荧光强度的变化、溶剂效应对其荧光性能的影响以及酸性条件下荧光光谱的变化。结果表明,MDCM和BDCM的最大荧光发射波长均在红光区域,2种化合物溶液的最大荧光发射波长随溶剂极性和溶液酸性的增强而发生红移,由于浓度猝灭效应,MDCM和BDCM的DMF溶液浓度分别为1×10-4和1×10-5mol/L时,荧光发射峰为最强。又因为BDCM分子的共轭度比MDCM大得多,所以其固体的最大荧光发射波长向长波长移了37nm。     

新型苯并香豆素醛的设计合成及光物理性质研究

设计合成了具有较长发射波长的苯并香豆素醛--8-二乙氨基-2-氧-2H-苯并香豆素醛(BCA),通过吸收和荧光光谱研究其在不同溶剂中的光物理性质.结果表明,BCA具有明显的溶致变色效应和宽的颜色变化范围.随着溶剂极性的增加,其荧光发射可从蓝绿光变到红光,而荧光量子效率则从0.98减小到0.26.     

两种新型芴类Schiff碱的合成及其溶剂效应和聚集诱导发光性质

2-氨基-9,9-二甲基芴分别与2-羟基-1-萘甲醛和4-二乙胺基水杨醛经Schiff碱反应合成了两种新型芴类Schiff碱 (4和5),其结构经¹H NMR, ¹³C NMR, ESI-MS和元素分析表征。通过紫外-可见吸收光谱和荧光发射光谱初步研究了4和5的溶剂效应和聚集诱导发光性质。结果表明： 4和5的紫外吸收和荧光光谱受质子性溶剂的影响明显高于非质子性溶剂,同时两者具有良好的聚集诱导发光增强效应。THF-H₂-O体系中含水量分别达到60%和70%时, 4和5的荧光强度最大。     

卤素取代与溶剂效应对荧光素的荧光光谱的影响

基于卤族元素对荧光素荧光性能的影响作用,采用甲磺酸为催化剂,分别以4-卤代(氟、氯、溴)间苯二酚为原料通过Friedel-Crafts酰化/环化脱水反应合成了2',7'-二卤代荧光素(DFF、DCF、DBF)。分析了不同卤族元素取代对荧光素的紫外-可见吸收和荧光发射光谱的影响,结果表明,与荧光素光谱相比,氟原子和氯原子取代对增强荧光发射强度效果明显,溴原子的引入降低荧光发射强度。考察了荧光染料浓度对其荧光强度的影响,结果发现,三种卤代荧光染料的浓度在1×10-5mol/L时均具有最大荧光发射强度。研究了染料的溶剂效应,发现荧光光谱随溶剂类型而变化,在极性溶剂中染料的荧光强度高、荧光发射波长较长,此外,在极性质子溶剂中斯托克斯位移比极性非质子溶剂中的大。     

吲哚类硼氟染料的合成及其光谱性能研究

以1H-2-吲哚甲酸为原料合成1H-2-吲哚甲醛,再与苯偶酰、苯胺合成了新型的硼氟荧光染料,并通过1H NMR,13C NMR对结构进行了鉴定。该化合物的紫外-可见吸收光谱及荧光光谱测试表明:该染料有较高的荧光量子产率,相对较大的Stokes位移;且荧光性能呈现明显的溶剂效应。     

High boron content carboranyl-functionalized aryl ether derivatives displaying photoluminescent properties

The reaction of alpha,alpha'-bis(3,5-bis(bromomethyl)phenoxy-p-xylene (3) with 4 equiv of the monolithium salt of 1-Ph-1,2-C2B10H11 or 1-Me-1,2-C2B10H11 gave the corresponding neutral carboranyl-functionalized aryl ether derivatives closo-4 and closo-5, respectively. These compounds contain four closo clusters that were degraded using basic conditions with KOH in EtOH, affording the corresponding nido-6 and nido-7 as potassium salts. Nido species were also isolated with tetramethylammonium as cation giving compounds nido-8 and nido-9 in good yield. The potassium salts showed good solubility in water and polar solvents. All these compounds were characterized by 1H, 11B and 13C NMR spectroscopy and UV-vis. The electronic data in different solvents indicated a solvatochromic shift for all compounds and a red shift of the absorption maxima for the nido species with respect to the closo derivatives. These neutral and anionic carboranyl-functionalized aryl ether derivatives represent a new family of high boron content luminescent compounds that show strong fluorescence emission in different solvents at room temperature. This phenomenon is very interesting considering the fact that none of the precursors have such a property. The fluorescence emission depends on the cluster substituent (Ph or Me) and the solvent polarity. Additionally, the fluorescence emission intensity was clearly dependent on the solvent polarity; the closo species showed strongest fluorescence intensities in the non-polar solvents, while anionic species were highly emissive in polar solvents.     

激基缔合物和激基复合物的形成及溶剂效应的研究

测试了ω-对联苯基多亚甲基羧酸4-[5′-对联苯基-1,3,4-(口恶)二唑基-2′-]苄酯及其模型化合物2-对甲苯基-5-联苯基-1,3,4-,(口恶)二唑在不同极性溶剂中的荧光发射光谱。它们既能形成分子间的激基缔合物又能形成分子内的激基复合物和三分子激基复合物。实验结果表明,溶剂极性的增加,有利于分子内激基复合物和三分子激基复合物的形成。     

2-(取代苯乙烯基)-5-取代苯并噁唑的合成及其光性能的研究

通过2-甲基苯并噁唑或2-甲基-5-叔丁基苯并噁唑在KOH/DMF介质中与苯甲醛或取代苯甲醛反应,合成了22个标题化合物,其中13个未见报道。测定了它们的结构和紫外光谱、荧光光谱、荧光量子产率,并对母体化合物的溶剂效应进行了研究。     

Two Dehydroabietic Acid-based Arylamines: Synthesis, Crystal Structure and Fluorescent Properties

Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-Vis absorption and fluorescence spectral characteristics of these compounds in methanol were investigated. Their fluorescence emission spectra in different polarity solvents were further evaluated. Fluorescent properties and structural relationship of the compounds showed that fluorescence intensity and quantum yield inversely increase with the non-coplanar degree. In addition, the solvent polarity has different effects on the fluorescence emission spectra of two compounds.     

Microwave-assisted Catalyzed Synthesis and In vitro Bioactivity Evaluation of Benzimidazoles Bearing Phenolic Hydroxyl

An efficient and facile method was introduced for the synthesis of benzimidazoles in this paper. The optimum reaction conditions were determined. A series of benzimidazoles bearing phenolic hydroxyl(2a-2t) were synthesized in moderate to excellent yields starting from differently substituted hydroxyl benzaldehyde and 4-position substituted o-phenylenediamine via nucleophilic addition in the presence of catalyst Na₂S₂O₅ under microwave irradiation condition. Herein, effects of the catalyst, molar ratio of reactants, reaction temperature and solvent were investigated. The optimal reaction condition was determined. The effect of DMF and EtOH solvent on the reaction was compared. The synthesized compounds were characterized by FTIR, HRMS, ¹H NMR and ¹³C NMR spectroscopy. Further, the bacteriostatic activities of the synthesized compounds were evaluated with ciprofloxacin and itraconazole as a positive control, respectively. Compounds 2b, 2n, 2q and 2r exhi-bited some antibacterial activity. The lowest MIC of antibacterial activity of compound 2b was 32 μg/mL. Meanwhile, the luminescence property of compound 2b was studied. The antibacterial activity of compound 2b, along with their good fluorescence performance highlighted the potential of these compounds as lead structures and owned fluorescence trace for further study towards the development of novel drugs and functional mechanisms in living organisms.     

Photochromism of new 3,5-position hybrid diarylethene derivatives bearing both thiophene and thiazole moieties

Five new diarylethenes based on a hybrid structure of bis(5-thiazolyl)ethene and bis(3-thienyl)ethene were synthesized, and the structures of the four compounds were determined by single-crystal X-ray diffraction analysis. The properties of these diarylethenes, such as photochromism, fluorescence, and electrochemical properties were investigated in detail. All of these compounds showed good photochromism and fluorescence both in solution and in PMMA films. The electron-donating substituents could effectively increase the cyclization and cycloreversion quantum yields, and the fluorescence emission peaks, whereas the electron-withdrawing groups functionalized an inverse action for these diarylethene derivatives. Cyclic voltammetry revealed that great differences existed amongst the electrochemical behaviors of these compounds. The oxidation potentials and the band gaps of these diarylethenes increased remarkably with the increase in electron-withdrawing ability. All results suggested that the effects of substitution have a significant effect on the photochemical and electrochemical behaviors of these diarylethene derivatives.     

芳杂环推拉型大分子的多光子上转换荧光性质

用Wittig反应和Heck反应制备了2个新的芳杂环推-拉型荧光大分子聚[(2,5-二苯撑-1,3,4-噁二唑)-4,4'-乙烯撑-交替-N,N'-二(4-苯乙烯撑)]苯胺(P1)和聚[(2,5-二苯撑-1,3,4-噁二唑)-4,4'-乙烯撑-交替-N-乙基-3,6-咔唑乙烯撑](P2). P1和P2的分解温度分别为373和412 ℃, 热稳定性良好. 电化学性能用循环伏安法测定. P1和P2的最高占有分子轨道(HOMO)能级分别为-5.39和-5.81 eV, 最低未占有分子轨道(LUMO)能级分别为-2.81和-3.09 eV. 用飞秒Ti:Sapphire激光器测定了P1和P2的三光子和双光子上转换荧光光谱. 在1250 nm波长激发下, 在四氢呋喃溶液中P1和P2的三光子荧光发射峰分别位于510和491 nm. 在800 nm波长激发下, 在四氢呋喃溶液中P1和P2的双光子荧光发射峰分别位于511和495 nm. 在四氢呋喃溶液中大分子P1和P2单光子荧光发射峰分别位于503 和475 nm, P1和P2的荧光量子产率分别为0.80和0.31. 研究了多光子荧光发射过程的溶剂效应. 结果表明, 溶剂极性增大, P1和P2的多光子荧光发射波长明显红移.     

3,14‐Bis(p‐nitrophenyl)‐17,17‐dipentyltetrabenzo[a,c,g,i]‐fluorene: A New Fluorophore Displaying Both Remarkable Solvatochromism and Crystalline‐Induced Emission

A series of 17,17‐dialkyl‐3,14‐diaryltetrabenzofluorenes were efficiently prepared by using Suzuki–Miyaura cross‐coupling reactions of the corresponding 3,14‐dibromo derivatives. Studies of the unique fluorescence properties of these compounds showed that they display intense blue to yellow fluorescence with high quantum yields in the solution state and blue to orange fluorescence with moderate quantum yields in the solid state. In addition, the fluorescence wavelength of the bis(p‐nitrophenyl) derivative is remarkably solvent‐dependent in a manner that correlates with the solvent polarity parameter E_T(30). The results of density function theory calculations suggest that the intramolecular charge‐transfer character of the HOMO–LUMO transition is responsible for the large solvent effect. Moreover, addition of water to a tetrahydrofuran (THF) solution of this compound leads to quenching of the yellow fluorescence owing to an increase in the solvent polarity. However, when the amount of water fraction exceeds 70 %, a new fluorescence band appears at the same orange‐red emission wavelength as that of the solid‐state fluorescence. This observation suggests the occurrence of a crystallization‐induced emission (CIE) phenomenon in highly aqueous THF.     

Synthesis and spectroscopic characterization of two tetrasubstituted cationic porphyrin derivatives

An imidazolium tetrasubstituted cationic porphyrin derivative (the free base and its Zn(II) complex) with five-membered heterocyclic groups in the meso-positions were synthesized using microwave irradiation, and the compounds obtained characterized by (1)H-NMR and mass spectrometry. We observed that under microwave irradiation the yield is similar to when the synthesis is performed under conventional heating, however, the time required to prepare the porphyrins decreases enormously. In order to investigate the electronic state of these compounds, we employed UV-Vis and fluorescence spectroscopy combined with quantum chemical calculations. The results reveal the presence, in both compounds, of a large number of electronic states involving the association between the Soret and a blue-shifted band. The Soret band in both compounds also shows a considerable solvent dependence. As for emission, these compounds present low quantum yield at room temperature and no solvent influence on the fluorescence spectra was observed.     

FLUORESCENCE AND ELECTROGENERATED CHEMILUMINESCENCE STUDIES OF SEVERAL DIMETHYL-SUBSTITUTED BENZO[a]PYRENES

Abstract— Absorption spectra, molar absorptivities, fluorescence spectra and fluorescence quantum yields of five dimethylbenzo[a]pyrenes (DMBP) in benzene solutions at room temperature are reported. Electrogenerated chemiluminescence (ecl) spectra and the relative eel intensities of these compounds to that of 9,10-diphenylanthracene in the 1:1 acetonitrile-benzene mixed solvent with tetra- n -butyl-ammonium perchlorate as a supporting electrolyte are also reported. Both fluorescence quantum yield and ecl intensity studies show that the vicinal dimethyl substitution lowers the fluorescence and eel efficiency, and this effect is more pronounced in a compound whose K-region is blocked. The compounds in which the L-region is blocked showed much higher fluorescence and eel efficiency. The fluorescence of DMBP molecules is quenched by the donor molecule, tri- p -tolylamine with a diffusion controlled rate to form an emitting exciplex. The cation radical of TPTA and the radical anion of the DMBPs are shown to form an exciplex efficiently by the eel experiments. Both quenching and eel results indicate that all DMBPs studied here are good acceptors.