Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

光束发散度对紫外写入光纤光栅的影响

用傅里叶衍射光学分析了准分子激光束发散度对于光纤光栅制备的影响，发现光束发散角使光纤光栅的布拉格波长发生改变，相位版后干涉场沿光纤轴向和径向不均匀，对制备30dB高反射率光纤光栅造成困难。实验结果与理论分析基本一致，相对于理想平行光束情况，会聚光束使得光纤光栅布拉格波长出现在短波一边，发射光束使得光纤光栅布拉格波长出现在长波一边。     

Quinone imine dye formation via photocycloaddition between isocyanates and chloranil

Photochemical [2+2]cycloaddition between electron-donating aryl isocyanates and chloranil was observed in acetonitrile or benzene, and the following elimination of carbon dioxide resulted in the formation of the corresponding quinone imine dyes. This new route for synthesis of quinone imine was investigated by product analyses, laser flash photolyses, and molecular orbital calculation.     

Electronic structure of the wrong-bond states in amorphous germanium sulphides

First-principles calculations of the electronic structures of the wrong bonds were performed for amorphous germanium sulphides in order to explain their compositional dependence. Model cluster calculations of the density of states using a set of geometry similar to the crystalline-GeS₂ coordination can reproduce the peak structure of the experimental valence band photoemission spectra. The bonding and anti-bonding states of the covalent Ge-S bonds form valence and conduction band respectively, and the top of the valence band is occupied with S 3p lone-pair states. The bonding states are modified by S-S bonds and the anti-bonding states are modified by Ge-Ge bonds, mainly through their hybridization with the wrong-bond states between p-orbitals. The lone-pair states do not interact either of them to form a different band, and obscure the modification induced by the S-S wrong bonds. Therefore, we can conclude that the narrowing of the bandgap with increasing Ge content from GeS₂ composition is due to that of the conduction-band bottom with increasing germanium wrong bonds, though the narrowing with increasing S content is moderate due to the presence of the lone-pair states at the valence-band top.     

Photochemical deprotection of nitro-substituted benzenesulfenates via photoinduced electron transfer

The photochemical deprotection of alkyl 2,4-dinitrobenzenesulfenate or alkyl 2-nitrobenzenesulfenate was successfully achieved by addition of triethylamine, while it was unsuccessful without triethylamine. The sulfur-oxygen bond cleavage is thought to occur heterolytically in the sulfenate anion radical produced by photoinduced electron transfer with triethylamine.     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

Model and empirical study on some collaboration networks

In this paper we present an empirical study of a few practical systems described by cooperation networks, and propose a model to understand the results obtained. We study four non-social systems, which are the Bus Route Networks of Beijing and Yangzhou, the Travel Route Network of China, Huai-Yang recipes of Chinese cooked food, and a social system, which is the Collaboration Network of Hollywood Actors. In order to explain the results related to the degree distribution, act-degree distribution and act-size distribution (especially about the degree distribution, which may be better fitted using a stretched exponential distribution (SED)), we suggest a simple model to show a possible evolutionary mechanism for the emergence of such networks. The analytic and numerical results obtained from the model are in good agreement with the empirical results.     

Exponential approximations in the classes of life distributions

In this paper we discuss the approximation of life distributions by exponential ones. The main results are: (1) F NBUE, where its mean is 1, we have , 0, where = 1 - ₂/2, ₂ being the second moment ofF. The inequality is sharp. (2) In the case ofFIFR, the upper bound is . (3) For the HNBUE class, the upper bound is min . Furthermore, the improved upper bound is . In addition, we show 0} |\bar G(t) - e^{ - t} | \leqslant \sqrt {\frac{\rho }{2}} $$ " align="middle" border="0"> , where (4) For the IMRL class, the upper bound is /(1+) ([1]). Here we give a simple proof.Project supported by the National Natural Science Fund of China.