固液态均荧光发射的四苯乙烯基衍生物的合成

为了打破传统荧光材料的聚集荧光淬灭(ACQ)的应用限制,通过共价键连接聚集诱导发光(AIE)分子与平面ACQ分子,可以构建在溶液中和固态下都具有荧光发射特性的化合物。分别通过多步反应合成了带有烷基硫醚的萘酰亚胺衍生物3和连接炔吡啶的四苯乙烯衍生物7。化合物3和化合物7通过酰胺缩合,合成了一种四苯乙烯-萘酰亚胺二联体化合物8,化合物8兼具ACQ和AIE分子的特性。结果表明：溶液状态下化合物8具有蓝色荧光发射,其最大发射峰位于452 nm,固态下为黄绿色荧光,最大发射峰位于487 nm。利用三氟乙酸对其荧光进行调控能够实现CIE色坐标为(0.33, 0.32)的单分子白光发射。     

氨基与冠醚双官能团四苯乙烯衍生物自组装及其聚集诱导荧光研究

冠醚和二级铵盐结构的分子经常被用来构建超分子自组装体,报道了一种不对称的四苯乙烯衍生物单体,其分别与二苯并-24-冠-8(DB24C8)和二级铵盐结构单元通过点击化学反应连接,通过核磁共振氢谱、碳谱和质谱得到结构表征.通过核磁滴定显示出冠醚和二级铵盐结构在酸性条件下能够形成超分子组装体,并初步研究了其在乙腈/水溶液中的聚集诱导荧光性能.     

四苯乙烯衍生物与大环主体在主客体相互作用下的聚集诱导发光

具有聚集诱导发光性质化合物的发展不仅很大程度上解决了传统有机分子发色团在高浓度、固态或者薄膜等形式的聚集状态下荧光猝灭的问题,而且扩展了有机发色团在荧光探针、传感器以及细胞成像等方面的应用。其中,四苯乙烯及其衍生物作为具有聚集诱导发光性质的典型化合物已被广泛应用在材料化学、生物化学等相关研究领域。受此启发,超分子化学家也将这类具有聚集诱导发光性质的四苯乙烯及其衍生物作为研究对象引入到超分子化学的领域,特别是利用大环主体与四苯乙烯客体通过主客体相互作用有效地限制了荧光客体分子的分子内转动或运动,增强了这类超分子体系的发光强度,并为其在刺激响应性传感器、智能探针等方面提供了新思路。本文总结了近年来涉及四苯乙烯衍生物与大环主体通过主客体相互作用形成聚集诱导发光超分子体系的发展,并按照大环主体进行分类简要介绍其应用。     

咔唑基四苯乙烯多功能发光材料的合成与性能

设计合成了一个以四苯乙烯为核心,四端连接长烷基链的咔唑基四苯乙烯衍生物(TPECz),该化合物具有典型的聚集诱导发光(AIE)特性.紫外光谱(UV-Vis)、荧光光谱(PL)、热重(TG)和示差扫描量热(DSC)研究表明,该化合物属于深蓝光材料、具有较好的热稳定性,并且对金属Fe3+具有很好的识别作用,有望用于金属离子检测;同时,该化合物外围的咔唑基团具有电化学活性,采用电化学聚合方法可制备其聚合物交联荧光薄膜,扫描电镜(SEM)和原子力显微镜(AFM)研究表明,该荧光薄膜表面平整,有望用于制备有机电致发光器件(OLED),可见该化合物是一种多功能材料.     

硅烷桥联四苯乙烯-寡聚噻吩衍生物的结构与光谱性质（英文）

设计合成了一系列硅烷桥联四苯乙烯(TPE)-寡聚噻吩衍生物.硅烷取代基为甲基和苯基,寡聚噻吩单元中噻吩数量为1～3,通过空间位阻效应和电子效应调控分子的固态发光性质.具有苯基取代基的硅烷和二噻吩分子表现出高达64.5%的固态发光.含1或2个噻吩单元的分子的固态和液态荧光性质类似四苯乙烯,而含3个噻吩的分子的发光则主要来自于三噻吩,其在液态和聚集态分别有1.4%和14%的发光效率.苯基硅烷桥联三噻吩-四苯乙烯分子的聚集体具有检测硝基爆炸物的能力和防伪应用潜力.     

ATRP合成星型聚4-乙烯基二苯乙烯及性能研究

本文以2-溴异丁酸季戊四醇四酯(PT-Br)为引发剂,CuBr为催化剂,五甲基二亚乙基三胺(PMDETA)为配体,引发荧光单体4-乙烯基二苯乙烯(VS)进行原子转移自由基聚合,合成了星型荧光聚合物,且分子量分布较窄(1.37～1.50).通过与线性聚4-乙烯基二苯乙烯(line-PVS)的性能比较,发现星型聚4-乙烯基二苯乙烯的溶液粘度和玻璃化转变温度都相对较低.另外,还通过荧光光谱对星型聚合物的光学性能进行了表征.     

8-羟基喹啉衍生物及其金属配合物的合成与光致发光特性

设计合成了三种新型的8-羟基喹啉衍生物配体: 5-[(4-E-苯乙烯基)-苯甲亚胺基]-8-羟基喹啉(1), 5-[(4-溴-2-氟)-苯甲亚胺基]-8-羟基喹啉(2)和N-乙基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑(3), 以及它们相应的金属配合物, 产物经质谱(MS)、元素分析(EA)、红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱(¹H NMR)进行表征, 并测定了它们的荧光性质. 结果与8-羟基喹啉比较表明, 5位和2位取代8-羟基喹啉衍生物的荧光发生了明显的红移. 同时测定了配合物(3)₂Zn的荧光寿命, 结果表明, N-乙基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑锌配合物表现出较长的荧光寿命.     

二苯乙烯基蒽衍生物:聚集诱导发光性质、机理及应用

与传统的发光分子相比,具有聚集诱导发光(AIE)性质的分子,在聚集态或固态条件下,由于独特的分子结构和聚集态结构,表现出显著增强的荧光发射,因而在光电器件、生物化学检测等领域展现出广阔的应用前景。本文总结了二苯乙烯基蒽(DSA)及其衍生物的AIE性质,分析了DSA类分子AIE现象的机理,如分子内转动受限、扭曲的分子结构及分子间聚集结构等,同时介绍了此类分子在固态发光、刺激-响应材料,以及生物检测和生物成像等方面的应用。     

含三氟苯基8-羟基喹啉锌配合物的合成及紫外、荧光性能对比研究

设计合成了两种含三氟苯基的新型8-羟基喹啉衍生物配体:(E)-2-[2-(2,4,6-三氟苯基)乙烯基]-8-羟基喹啉(B)、(E)-5-[2-(2,4,6-三氟苯基)亚胺基]-8-羟基喹啉(C)及其相应的锌配合物D与E,产物经NMR,IR,MS,元素分析等进行结构表征。通过核磁、紫外滴定跟踪了金属锌与配体的配位过程,并测定了两者溶液状态下的荧光性质:化合物D,E在甲醇溶液中的荧光发射峰位置分别在599 nm和572 nm处;相比于8-羟基喹啉,2位和5位取代8-羟基喹啉衍生物的荧光发生了明显红移。锌配合物固体荧光寿命的测定结果表明,配合物D表现出较长的荧光寿命。     

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.     

Spectral-luminescence and generation characteristics of 1-R-vinyl-3-aryl(heteryl)benzo[f]quinolines

The absorption and fluorescence spectra and the fluorescence quantum yields of 1-R-vinyl derivatives of benzo[f]quinoline containing aryl and 2-, 4-, and 6-quinolyl groups in the vinylene grouping and in the 3 position were studied. The relationship between the spectral-luminescence characteristics and the structures of the molecules was examined. It was established that solutions of compounds that contain a dimethylamino group attached to the phenyl ring give forced emission when they are excited with the second harmonic of a ruby laser. The effect of the solvent on the spectral-luminescence and generation characteristics of the indicated compounds was investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 511–515, April, 1978.     

Antiplatelet α-Methylidene-γ-butyrolactones: Synthesis and evaluation of quinoline,flavone, and xanthone derivatives

As a continuation of our previous studies on the synthesis and antiplatelet activity of coumarin derivatives of α-methylidene-γ-butyrolactones, certain quinoline, flavone, and xanthone derivatives were synthesized and evaluated for antiplatelet activity against thrombin (Thr)-, arachidonic acid (AA)-, collagen (Col)-, and platelet-activating factor (PAF)-induced aggregation in washed rabbit platelets. These compounds were synthesized from quinolin-8-ol, flavon-7-ol, and xanthon-3-ol, respectively, via alkylation and Reformatsky-type condensation (Schemes 1–3). By the comparison with comparison with coumarin α-methylidene-γ-butyrolactone 3a , flavone and xanthone derivatives, 3b and 3c , respectively, are more selective in which only AA- and collagen-induced aggregation are strongly inhibited. Most of the quinoline derivatives ( 9a–e ) exhibited broad-spectrum antiplatelet activities.     

Photophysical properties of novel ferrocenyl quinoline derivatives with red emission in solutions and polymeric matrices

A group of novel 2-ferrocenyl quinoline derivatives was designed and their photophysical properties were thoroughly studied. UV-VIS and steady-state fluorescence spectra show that these compounds gain energy in the ultra-violet region and give red emissions in different organic solvents. More importantly, two transparent hybrid thick films composed of 2-ferrocenyl quinoline and poly[1-(methoxycarbonyl)-1-methylethylene] (poly(methyl 2-methylpropenoate, (poly(methyl methacrylate), PMMA), or poly[2-hydroxyethyl 2-methylprop-2-enoate] (poly(2-hydroxyethyl methacrylate), PHEMA) matrix were successfully prepared. Both films showed red emissions of ferrocenyl quinoline chromophore and the ideal composition of luminescent species is 10⁻⁶ M PMMA and 10⁻⁵ M PHEMA, respectively. SEM graph exhibited ferrocenyl quinoline molecules dispersed very homogenously within the above polymer hosts.     

Time-resolved total internal reflection fluorescence spectroscopy. Part I. Photophysics of Coumarin 343 at liquid/liquid interface

Pico-second time-resolved time-correlated single photon counting (TCSPC) technique under the total internal reflection (TIR) condition has been used to study the photophysical properties of Coumarin 343 (C343) dye molecules adsorbed at the water/1,2-dichloroethane (DCE) interface. The fluorescence decay profile of C343 under TIR condition at the water/DCE interface was non-exponential and fitted to the double exponential decay function with the fluorescence lifetimes 0.3 and 3.6 ns, which proved the existence of two different forms of C343 species having largely different lifetimes at the interface. The longer fluorescence lifetime component of C343 at the interface is attributed to the emission from the monomeric form of the dye molecules and the shorter lifetime component is due to the aggregation of dye molecules. The penetration depth dependence of decay curves indicated no change in the fluorescence lifetime components, however, the amplitude corresponding to the lifetime of aggregate increased and the amplitude corresponding to the lifetime of monomer decreased with the decrease in penetration depth of the aqueous phase from the interface. Aggregation is significant in the interfacial layer. The decrease in monomer lifetime at the interface compared to that in the bulk solution is interpreted in terms of excitation energy migration between the dye molecules.     

Modulating affinities of di-2-picolylamine (DPA)-substituted quinoline sensors for zinc ions by varying pendant ligands

We have developed a series of di-2-picolylamine (DPA)-substituted quinoline sensors, HQ1- 4, bearing a pendant ligand at the 8 position of quinoline. UV-vis spectra of HQ1- 4 showed similar variations to that of HQ5 but with different varying extents upon the titration of zinc ions. Fluorescence intensities of HQ1, HQ3, and HQ4 were enhanced 4-6 times upon the addition of 1 equiv of zinc ions under an aqueous buffer. Somewhat unexpectedly, HQ2 is nonfluorescent in the presence of metal ions, including zinc ions. The affinities of HQ sensors are distributed in a broad range from nanomolarity to femtomolarity by varying the pendant ligands near the coordination unit. More importantly, these new sensors exhibited very high selectivity for Zn(2+) over Na(+), K(+), Mg(2+), and Ca(2+) at the millimolar level and over other transition metal ions at the micromolar level, except for Cd(2+). These findings indicated that the incorporations of the pendant groups exerted no effect on the spectroscopic properties and selectivity of the parent fluorescent sensor, with the exception of HQ2. Finally, X-ray crystal structures of ZnHQ's revealed that the auxiliary pendant groups at the 8 position participated in zinc coordination and were able to tune the affinities of HQ sensors.     

具有聚集诱导发光性能的乙烯基衍生物的合成及其对DNT的检测

采用Wittig-Horner反应合成了两种具有聚集诱导发光(AIE)性能的乙烯基衍生物.紫外及荧光光谱显示,两种化合物在聚集态时分子间的π-π相互作用很弱,二者在聚集态时都展示了很强的荧光增强发光性能.由于二者所具有的扭曲的分子构型提供了2,4-二硝基甲苯(DNT)气态分子扩散所需的分子通道,因此对DNT蒸气的检测均显示了较高的荧光猝灭效率,且其荧光猝灭具有较好的可逆性.     

Photoactivatable Aggregation‐Induced Emission Fluorophores with Multiple‐Color Fluorescence and Wavelength‐Selective Activation

Photoactivatable (caged) fluorophores are widely used in chemistry, materials, and biology. However, the development of such molecules exhibiting photoactivable solid‐state fluorescence is still challenging due to the aggregation‐caused quenching (ACQ) effect of most fluorophores in their aggregate or solid states. In this work, we developed caged salicylaldehyde hydrazone derivatives, which are of aggregation‐induced emission (AIE) characteristics upon light irradiation, as efficient photoactivatable solid‐state fluorophores. These compounds displayed multiple‐color emissions and ratiometric (photochromic) fluorescence switches upon wavelength‐selective photoactivation, and were successfully applied for photopatterning and photoactivatable cell imaging in a multiple‐color and stepwise manner.     

Photophysical properties of 9,10-disubstituted anthracene derivatives in solution and films

We have carried out absorption, time-resolved fluorescence, and fluorescence quantum yield measurements of four new soluble anthracene derivatives. They show natural radiative lifetimes in the range of 2.5-4.4 ns, which is 5-10 times shorter than those reported for unsubstituted anthracene. The 9,10-bis(phenylethynyl)anthracene (BPEA) derivatives show the largest fluorescence transition dipoles, which is attributed to extended π-conjugation between anthracene and phenyls through acetylene linkages. Spin-cast films of the BPEA derivatives show strong fluorescence quenching by weakly emitting low energy excitations, which is attributed to excimer-like traps. Quenching is significantly reduced when bulky dendrons are attached so that they give maximum coverage of the emitting chromophore and prevent their aggregation. The results show that anthracene derivatives can be developed into efficient solution-processable fluorescent emitters for the blue and green spectral regions.     

Two—photon Excited Fluorescence of Bithiophene Derivatives

Two new bithiophene derivatives named as 5,5‘‘-bis(p-N,N-dimethylaminostyryl)-2,2‘-bithiophene (BMSBT),and 5,5‘-bis(p-N,N-diethylaminostyryl)-2,2‘-bithiophene (BESBT) have been synthesized.Both compounds can emit strong single-photon excited fluorescence (SPEF) and two-photon excited fluorescence (TPEF) with the emission peaks around-560nm and with the lifetime of-1ns.