Synthesis,Characterization and Optoelectronic Property of Axial-Substituted Subphthalocyanines

Two novel substituted subphthalocyanines have been prepared introducing m-hydroxybenzoic acid and m-hydroxyphenylacetic acid into the axial position of bromo-subphthalocyanine. The compounds have been characterized by Fourier transform infrared (FT-IR), Nuclear Magnetic Resonance (NMR) and single-crystal X-rays diffraction (XRD) methods. Their photophysical properties show that the axial substitution results into a relatively higher fluorescence quantum efficiency (Φ_F=5.74 for m-hydroxybenzoic acid and 9.09 % for m-hydroxyphenylacetic acid) in comparison with that of the prototype compound, despite the almost negligible influence on the maximum absorption or the emission position. Moreover, the electrochemical behaviors show that the axial-substituted subphthalocyanines also exhibit enhanced specific capacitances of 395 F/g (m-hydroxybenzoic acid) and 362 F/g (m-hydroxyphenylacetic acid) compared with 342 F/g (the prototype) to the largest capacitance at the scan rate of 5 mV/s, and the significantly larger capacitance retentions of 83.6 % and 82.1 % versus 37.3 % upon density up to 3 A/g. These results show the potential of these axial-substituted subphthalocyanines in the use as organic photovoltaics and supercapacitors.     

取代效应对脂滴检测NAPBr染料分子的双光子吸收和激发态性质影响的理论探究（英文）

双光子荧光染料分子在生物医学成像中具有广阔的应用前景,但取代效应对分子结构以及光物理性质影响的探求相对匮乏.本文设计并研究了一系列脂滴检测染料分子,分析了分子的光学性质以及无辐射跃迁等.通过分子内弱相互作用和电子-空穴布居分析,阐述了其内在机理.结果表明,所研究的分子均具有优良的光物理性能、高效荧光量子产量、大的斯托克斯位移以及显著的双光子吸收截面等.本工作合理地解释了实验现象并阐述了取代效应对脂滴检测NAPBr染料分子的双光子吸收和激发态性质的影响,这为设计新型的高效有机分子提供了理论指导.     

Theoretical study on photophysical properties of phenolpyridyl boron complexes

Organoboron complexes have potential application in organic light-emitting devices (OLEDs). Our group has synthesized four phenolpyridyl boron complexes (Inorg. Chem. 2006, 45, 2788), which can function as an electron transport materials (ETM), white and blue emitters, and exhibit high efficiency and stability. To reveal the relationship between the properties and structures of these functional materials, theoretical analysis of spectral properties and electronic structures of these complexes was systematically characterized with the B3LYP and 6-31G* basis set. The calculated absorption and emission spectra of these systems are in good agreement with the experimental ones. It is clear seen that these transitions are charge transferred along 2,6-bis(2-hydroxyphenyl)pyridyl boron moiety, and the contribution of boron atom in these compounds to the main transition orbitals is vanishingly small. The substitution of methyl and methoxyl for hydrogen does not change the absorption wavelengths and transition natures, but influences the radioactive efficiencies and electron transport properties, which are observed and discussed in detail. Furthermore, large red shifts of fluorescence are caused by replacing the hydrogen with CN or NO2 groups, which indicates that they are potential candidates as green-light-emitting materials. These results are favorable to further understanding the photophysical properties of this kind of complexes.     

Ti和乳酸共改性α-Fe2O3光阳极光电化学性能研究

采用一步水热后在氮气中进行热处理的方法制备了Ti和乳酸共改性的纳米花状α-Fe₂O₃光阳极。对样品分别进行了X射线衍射、扫描电镜、X射线光电子能谱、紫外-可见吸收光谱和光电化学性能测试。与乳酸改性的纳米片状α-Fe₂O₃光阳极相比,最优的Ti与乳酸共改性样品0.075LA-Fe2O3-0.75Ti光阳极的光电流密度从0.55mA·cm^-2提高到1.39mA·cm^-2。Ti改性明显减少了0.075LA-Fe₂O₃膜的表面态,增加了表面载流子注入效率;同时Ti的掺入也增加了电极体内载流子浓度,增强了体内载流子的传输效率。     

新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能

以2-二苯胺羰基苯甲酸(L)为第一配体,咪唑并[5,6-f]邻菲罗啉(IP)为第二配体,合成出新型稀土铕、铽三元配合物。采用元素分析、红外光谱、紫外-可见光谱对配体和配合物的结构进行了表征。红外光谱分析表明配合物中的稀土离子与第一配体L中的氧原子以及第二配体IP中的氮原子进行了配位。紫外光谱表明配合物主要是由第一配体L吸收能量。通过荧光光谱、荧光量子效率和荧光寿命研究了配合物的荧光性能,结果显示:两种配合物均表现出稀土离子的特征发射,且配合物的荧光量子效率和荧光寿命与发光强度成正比,配合物Tb(L)3IP的各项荧光性能均优于Eu(L)3IP。     

Promising fast energy transfer system via an easy synthesis: Bodipy-porphyrin dyads connected via a cyanuric chloride bridge, their synthesis, and electrochemical and photophysical investigations

The boron dipyrrin (Bodipy) chromophore was combined with either a free-base or a Zn porphyrin moiety (H(2)P and ZnP respectively), via an easy synthesis involving a cyanuric chloride bridging unit, yielding dyads Bodipy-H(2)P (4) and Bodipy-ZnP (5). The photophysical properties of Bodipy-H(2)P (4) and Bodipy-ZnP (5) were investigated by UV-Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. The comparison of the absorption spectra and cyclic voltammograms of dyads Bodipy-H(2)P (4) and Bodipy-ZnP (5) with those of their model compounds Bodipy, H(2)P, and ZnP shows that the spectroscopic and electrochemical properties of the constituent chromophores are essentially retained in the dyads indicating negligible interaction between them in the ground state. In addition, luminescence and transient absorption experiments show that excitation of the Bodipy unit in Bodipy-H(2)P (4) and Bodipy-ZnP (5) into its first singlet excited state results in rapid Bodipy to porphyrin energy transfer-k(4) = 2.9 × 10(10) s(-1) and k(5) = 2.2 × 10(10) s(-1) for Bodipy-H(2)P (4) and Bodipy-ZnP (5), respectively-generating the first porphyrin-based singlet excited state. The porphyrin-based singlet excited states give rise to fluorescence or undergo intersystem crossing to the corresponding triplet excited states. The title complexes could also be used as precursors for further substitution on the third chlorine atom on the cyanuric acid moiety.     

Near-infrared aminocyanine dyes: synthesis,optical properties,and application to the preparation of fluorescent microspheres

Several near-infrared (NIR) fluorescent dyes based on aminocyanine have been designed, synthesized, and used for preparation of NIR fluorescent microspheres. Their spectral properties and pH-dependent optical characteristics were investigated. It was found that different substitution at the central position of the dyes led to diverse optical properties, with especially large effects on their spectroscopic properties. Spectroscopic responses of the fluorescent dyes to changes of pH were different. Under acidic conditions, the wavelengths of maximum absorption of the N-substituted cyanine dyes were clearly red shifted. Dyes with an N-substituted piperazidine ring were the most sensitive. The fluorescent microspheres retained the properties of the parent dyes, making them suitable for applications in biological studies.     

敏化染料分子长径比对太阳能电池性能的影响

采用同一系列但分子长径比不同的3种染料:2-氰基-3-[2-[4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基氨基)-嘧啶-5-取代基]-丙烯酸(MTPA-Pyc)、2-氰基-3-(4-{2-[4-N,N-二(4-甲基苯基)氨基苯基]乙烯基}-苯基)-丙烯酸(MTPAcc)和2-氰基-3-[4-N,N-二(4-甲基苯基)氨基苯基]-丙烯酸(MTPAc),研究了在不同吸附溶剂中3种染料分子在Ti O2上的吸附量和聚集态,探讨了敏化染料分子长径比对染料敏化太阳电池性能的影响.结果表明,MTPAcc具有最合适的分子长径比,其在Ti O2表面的吸附量及应用的光电性能最高;吸附溶剂的极性增大有利于提高染料的吸附量,但也会影响染料分子的聚集态.当以四氢呋喃为吸附溶剂时,MTPAcc在Ti O2表面的吸附量大且不发生聚集,对应的敏化太阳能电池器件在所有结果中表现最好,在490 nm处的单色光光电转化效率(IPCE)极值达到84%,总光电转化效率(η)达到5.72%.     

磺酸肟酯类光产酸剂的制备及性能研究

本文合成了4种磺酸肟酯类非离子型光产酸剂,用核磁氢谱确认了产物结构,并测试了其热稳定性、紫外吸收特性及产酸效率.结果表明,合成的4种磺酸肟酯类光产酸剂在350-450 nm和深紫外区(DUV,248 nm)都有很好的吸收,在420 nm波段曝光下,(5-对三氟甲基苯磺酸酯亚胺-5H-噻吩-2-亚胺)-苯乙腈(P-2)产酸率最高,可达0.96;(5-对甲基苯磺酸酯亚胺-5H-噻吩-2-亚胺)-苯乙腈(P-1)在365 nm和420 nm两个波段下,均有较高的产酸率.利用实时红外(RT-IR)研究了相同浓度下4种光产酸剂对乙烯基醚化合物引发的光聚合动力学,同时研究了光产酸剂浓度对光聚合反应的影响,发现产酸剂浓度为2%时,光照30 s乙烯基醚化合物的双键转化率(DC%)即能达到80%.     

Side chain variations on a series of dicyanovinyl-terthiophenes: a photoinduced absorption study

We characterize a series of dicyanovinyl-terthiophenes with different alkyl side chains. Variations of side chain substitution patterns and length mainly affect the morphology of the evaporated thin films, which in turn sensitively influences properties like absorption, energy levels, and thin film roughness. To investigate changes in transfer processes between electron donor (D) and acceptor (A) molecules due to side chain variations, we use photoinduced absorption spectroscopy (PIA). PIA probes the long-living photoexcited species at the D-A interface: triplet excitons, cations, and anions. For a blend layer of dicyanovinyl-terthiophene and the electron acceptor fullerene C(60), an energy transfer via the singlet and triplet manifold of C(60) occurs. The recombination dynamics of the triplet excitons reveal two components that differ in their lifetime and generation rate by 1 order of magnitude. By comparing the dynamics of triplet excitons in neat and blend layers, we estimate the energy transfer efficiency in dependence of the type of side chain. The compound with methyl side chains shows remarkable properties regarding thin film absorption, surface roughness, and energy transfer efficiency, which we attribute to the specific nanomorphology of the thin film.     

ZnS光催化剂对不同偶氮类染料光降解的光催化性能的比较

在表面活性剂十六烷基三甲基溴化铵(CTAB)存在时,合成了ZnS光催化剂。 采用X射线衍射和透射电子显微镜等测试技术结果表明,制得的ZnS粒子尺寸均一,无团聚现象,平均粒径约为3.5 nm。 研究了ZnS光催化剂在紫外光下对不同染料的光催化降解效率,结果表明,ZnS光催化剂对一些含-N=N-基团的偶氮类染料,如甲基橙(MO)、酸性嫩黄(AY)、酸性橙Ⅱ(AOⅡ)光催化降解效率高达88％以上,甲基红(MR)的光催化降解效率也达59.63%。 表明-N=N-基团容易降解。 染料分子本身的吸光性也起一定的作用,虽然二甲酚橙(XO)和亚甲基蓝(MB)分子中均不含-N=N-基团,但由于XO的最大吸收峰分布于430 nm的紫外光区,其光催化降解效率可达43.83％,而MB最大吸收峰分布于664 nm可见光区,因此,其光催化降解效率则非常低。     

Synthesis of 1,4-dihydropyridines under solvent free conditions and investigation of their photo physical properties

Synthesis of five 4-aryl substituted 1,4-dihydropyridines was developed following condensation of multi component reaction strategy using yttrium triflate as a catalyst. The absorption and fluorescence properties of structurally related 4-aryl 1,4-dihydropyridines in different solvents of varied polarities was investigated. The absorption maxima of these compounds follow no order of solvent polarity and nature of substitution. The spectral characteristics are solvent and compound specific. Fluorophores with electron withdrawing group have larger fluorescence quantum yields and greater solvatochromism than the compounds with electron donating groups. Protic solvents yielded higher fluorescence quantum efficiency. The chemical shift of the proton attached to C-4 and the carbonyl stretching frequency of bis acetyl groups at 3 and 5-positions exhibited a linear relationship with Hammett's para substituent constants while no such relationship exists between the latter and electronic absorption maxima, fluorescence emission maxima, fluorescence quantum efficiency and Stokes shift.     

Novel carboxylated oligothiophenes as sensitizers in photoelectric conversion systems

Novel carboxylated oligothiophenes with different thiophene units were designed and synthesized as photosensitizers in dye-sensitized solar cells (DSSCs) for efficient opto-electric materials. The introduction of -COOH into thiophene molecules can lead to a red shift of UV-visible absorption, increase light-harvesting efficiency, and enhance photoinduced charge transport by forming efficient covalent bonds to the substrate surface. A red shift of the absorption spectrum of oligothiophene is also achieved by the increase in the number of thiophene units. The DSSCs based on the oligomers have excellent photovoltaic performances. Under 100 mW cm(-2) irradiation a short-circuit current of 10.57 mA cm(-2) and an overall energy conversion efficiency of 3.36 % is achieved when pentathiophene dicarboxylated acid was used as a sensitizer. The incident photo-to-current conversion efficiency (IPCE) has a maximum as high as 80 %. In addition, photovoltage and photocurrent transients show that slow charge recombination in DSSCs is important for efficient charge separation and excellent photoelectric conversion properties of the oligomers. These initial and promising results suggest that carboxylated oligothiophenes are efficient photosensitizers.     

Effects of Six‐Membered Carbohydrate Rings on Structure,Stability, and Kinetics of G‐Quadruplexes

We have evaluated the conformational, thermal, and kinetic properties of d(TGGGGT) analogues with one or five of the ribose nucleotides replaced with the carbohydrate residues hexitol nucleic acid (HNA), cyclohexenyl nucleic acid (CeNA), or altritol nucleic acid (ANA). All of the modified oligonucleotides formed G‐quadruplexes, but substitution with the six‐membered rings resulted in a mixture of G‐quadruplex structures. UV and CD melting analyses showed that the structure formed by d(TGGGGT) modified with HNA was stabilized whereas that modified with CeNA was destabilized, relative to the structure formed by the unmodified oligonucleotide. Substitution at the fourth base of the G‐tract with ANA resulted in a greater stabilization effect than substitution at the first G residue; substitution with five ANA residues resulted in significant stabilization of the G‐quadruplex. A single substitution with CeNA at the first base of the G‐tract or five substitutions with HNA resulted in striking deceleration or acceleration of G‐quadruplex formation, respectively. Our results shed light on the effect of the sugar moiety on the properties of G‐quadruplex structures.     

Two-dimensional bimetallic carbonyl cluster complexes with new properties and reactivities

The new electron-rich, anionic, planar cluster complex [IrRu(6)(CO)(23)](-), 5, isolated as a PPN salt, PPN = [Ph(3)PNPPh(3) ](+), has been synthesized and characterized crystallographically. The complex exhibits unusual absorption and emission properties. Computational analyses have been performed to explain its metal-metal bonding and electronic properties. Anion 5 reacts with [Ph(3)PAu][NO(3)] to yield the uncharged planar complex Ru(5)Ir(CO)(20)AuPPh(3), 6, by metal atom substitution.     

FDCA基聚酯的合成、性能及应用研究进展

生物质资源是一种储量丰富的可再生资源。生物质资源的高效利用不仅具有非常巨大的经济和生态价值,而且对新能源与生物基合成材料的可持续发展战略具有重大意义。由植物纤维素等生物质材料经生物或者简单化学过程处理,可获得丰富的生物基单体2,5-呋喃二甲酸(FDCA)。FDCA可用于生物基聚酯材料的合成。FDCA系列聚酯材料性能优异,可作为由石油基单体对苯二甲酸(PTA)而合成的芳香族聚酯材料(例如PET)的一种潜在的高性能生物可降解替代材料。本文简要说明了生物基单体FDCA的物性及制备方法,并重点阐述了包括聚呋喃二甲酸乙二酯(PEF)与聚呋喃二甲酸丁二酯(PBF)等一系列FDCA基聚酯材料的合成及性质,同时对FDCA基聚酯材料的应用进展进行了简要介绍,最后对FDCA基聚酯生物基合成材料的发展前景作了初步展望。     

STUDY ON THE ADSORPTION BEHAVIOR OF Pb(Ⅱ) ON NANOMETER ATTAPULGITE BY FAAS

The adsorptive behavior of nanometer attapulgite modified by acid to Pb(Ⅱ) was investigated by flame atomic absorption spectrometry (FAAS) in this paper. The mainly effect parameters on the adsorptive efficiency of Pb(Ⅱ), such as the acidity of the solution, the amount of attapulgite, oscillation time and static time were studied. Also the influencing factors of the recovery efficiency of Pb(Ⅱ), including the concentration of hydrochloric acid, the volume of hydrochloric acid, oscillation time and static time were investigated. The adsorptive capacity of Pb(Ⅱ) on nanometer attapulgite was 26.5mg/g and the adsorptive capacity of first cycle and second cycle regenerated nanometer attapulgite were 26.5mg/g and 26.3mg/g, respectively. The results obtained indicated that the regenerated effect was good.     

Spectral Properties of Fluorogenic Thiophene‐derived Triarylmethane Dyes

Spectral properties and fluorogenic behaviors of five novel thiophene variants of malachite green (MG), termed MGTs, were determined. Appreciable changes as a function of homologation and substitution pattern, including absorption band positions and intensities and fluorescence quantum yields were observed. In particular, the shorter wavelength y‐band absorption was found to shift over a nearly 200 nm range based on aryl group variation, allowing fine‐tuning of the excitation wavelength for these dyes. In addition, the fluorescence intensity of some MGTs increased significantly (up to 4600‐fold) when the dye was bound to a cognate protein partner, which is potentially useful for cell imaging studies.     

Substitution and condensation reactions with poly(anilineboronic acid): reactivity and characterization of thin films

Poly(anilineboronic acid) thin films are treated under various conditions to achieve substitution or condensation reactions involving the boronic acid moiety. These reactions are studied with polarization modulated infrared reflection absorption spectroscopy, cyclic voltammetry, and UV-vis spectroscopy. The results suggest the single-step formation of substituted polyanilines, such as poly(hydroxyaniline), halogenated polyanilines, and mercury chloride-substituted polyaniline. A condensation reaction of poly(anilineboronic acid) with cis-diol compounds in aqueous solution, as well as with phenylenebisboronic acid and salycilamide in THF, indicates the formation of boronic esters. The latter reactions appear to be a good entry point for the formation of complex or supramolecular polymer structures.