A new polymerization route for the preparation of functional heterocyclic polymers was developed from diphenol derivatives and unactivated internal diynes. The alkyne polyannulations of 4,4′-sulfonyldiphenol and 4,4′-(α,ω-alkylenedioxy)bis(diphenylacetylene)s or 1,2-bis[4-(2-phenylethynyl)phenyl]-1,2-diphenylethene were catalyzed by Pd(dba) in the presence of bathophenanthroline, silver acetate and copper(ii) acetate monohydrate in 1,4-dioxane at 130 °C, affording polymers with benzofuran moieties in satisfactory yields and high molecular weights (M up to 34-000). All the polymers were thermally stable, losing merely 5% of their weight at high temperatures of up to 376 °C. They showed a good film-forming ability and their thin solid films showed high refractive indices (RI = 1.900-1.611) in a wide wavelength region of 400-1000 nm. The polymer carrying tetraphenylethene units in the backbone was photosensitive and could be utilized to generate a fluorescent pattern by the photolithography process.

Zhang Yun    林荣业    唐本忠    

Polymer Chemistry

2016

Two novel phenylethene-carbazole derivatives containing dimesitylboron groups, 3-(dimesitylboryl)-9-ethyl-6-(1,2,2-triphenylvinyl)-9H-carbazole and 1,2-bis(6-(dimesitylboryl)-9-ethyl-9H-carbazol-3-yl)-1,2-diphenylethene are presented. The foregoing mono- and bis-carbazole containing compounds combine the aggregation-induced emission properties of phenylethene and the hole and electron transporting properties of carbazole and dimesitylboron substituents respectively. An extensive investigation of their optical and electrical properties reveals that these aggregation-induced emission active scaffolds exhibit excellent thermal stability (T up to 254 °C) with high electrochemical stability. Compared to our previous systems, the OLED device using the mono-carbazole derivative as a sky-blue emitter shows improved parameters such as the maximum luminance and maximum luminance efficiency of 13,930 cd m and 4.74 cd A, respectively. The device based on the blue-green emitting bis-carbazole derivative features equally high maximum luminance and maximum luminance efficiency of 15,780 cd m and 6.90 cd A, respectively.

Heping Shi    Li Min    Xin Dehua    Fang Li    Roose Jesse    Peng Huiren    Shuming Chen    唐本忠    

Dyes and Pigments

2016

Aggregation-induced emission (AIE) is a unique photo-physical phenomenon and has become an emerging and hot research area. With the enthusiastic efforts paid by researchers, hundreds of AIE-active luminogens (AIEgens) have been generated but heterocyclic AIEgens are rarely reported. Recently, we enriched the family of AIEgens and reported a pyrazine-based AIEgen of tetraphenylpyrazine (TPP), which could be facilely functionalized by a post-synthetic strategy. In this work, we further expanded the TPP-based AIE system by covalently attaching one, two or four electron-donating triphenylamine moieties to the TPP core via Suzuki coupling, and TPP-TPA, TPP-2TPA and TPP-4TPA were produced, respectively. Thanks to their donor-π-acceptor structures, these luminogens exhibit multi-functional properties, such as excellent thermal stability (up to 504°C), large molar absorptivity, bright emission in the solid state (quantum yields up to 35.2%), solvatochromism, and high two-photon absorption cross-sections (up to 480 GM). Furthermore, using TPP-TPA as the emitting layer, a triple-layer device was fabricated and a turn-on voltage, maximum luminance, current efficiency, power efficiency, and external quantum efficiency of 3.7 V, 17 459 cd m, 5.49 cd A, 3.18 lm W and 2.88% were realized, respectively. These results indicate a huge potential to develop high-tech applications based on these TPP-based AIEgens.

Chen Ming    Nie Han    Song Bo    Li Lingzhi    Jingzhi Sun    Anjun Qin    唐本忠    

Journal of Materials Chemistry C

2016

An AIE-based fluorescent nanoprobe (MTPE-M) has been developed and used for ratiometric detection of hypochlorite with high selectivity and sensitivity. More importantly, its application in live cells and zebrafish for ratiometric imaging of endogenous ClO has also been achieved.

Huang Yong    Peisheng Zhang    Gao Meng    曾钫    Anjun Qin    吴水珠    唐本忠    

Chemical Communications

2016

A tetraphenylethene (TPE) derivative modified with the strong electron acceptor 2-dicyano-methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) was obtained in high yield by a simple two-step reaction. The resultant TPE-TCF showed evident aggregation-induced emission (AIE) features and pronounced solvatochromic behavior. Changing the solvent from apolar cyclohexane to highly polar acetonitrile, the emission peak shifted from 560 to 680 nm (120 nm redshift). In an acetonitrile solution and in the solid powder, the Stokes shifts are as large as 230 and 190 nm, respectively. The solid film emits red to near-IR (red-NIR) fluorescence with an emission peak at 670 nm and a quantum efficiency of 24.8 %. Taking the advantages of red-NIR emission and high efficiency, nanoparticles (NPs) of TPE-TCF were fabricated by using tat-modified 1,2-distearoylsn-glycero-3-phosphor-ethanol-amine-N-[methoxy-(polyethyl-eneglycol)-2000] as the encapsulation matrix. The obtained NPs showed perfect membrane penetrability and high fluorescent imaging quality of cell cytoplasm. Upon co-incubation with 4,6-diamidino-2-phenylindole (DAPI) in the presence of tritons, the capsulated TPE-TCF nanoparticles could enter into the nucleus and displayed similar staining properties to those of DAPI.

Wang Yijia    Shi Yang    Wang Zhaoyang    Zhu    Zhao Xinyuan    Han Nie    Qian Jun    Anjun Qin    Jingzhi Sun    唐本忠    

Chemistry - A European Journal

2016

Organic electroluminescent materials that can simultaneously serve as light-emitting and electron-transporting layers in one organic light-emitting diode (OLED) are very useful for simplifying device configuration, but there are not many. In this work, three tailored luminescent materials (TPE-DB, TPE-BPDB and TPE-TPDB) adopting tetraphenylethene (TPE) and dimesitylboryl groups as the π-conjugated backbone and the electron-deficient functional group, respectively, are synthesized and fully characterized. Their thermal, photophysical, electronic, electrochemical, and electroluminescent properties are investigated systematically. The results reveal that these new dimesitylboryl-functionalized TPE derivatives feature aggregation-induced emission (AIE) characteristics with high fluorescence quantum yields of 81-86% in solid films. They possess high glass-transition temperatures of 134-168 °C and very low LUMO energy levels down to -2.9 eV. The OLED device [ITO/HATCN (20 nm)/NPB (40 nm)/TPE-DB (60 nm)/LiF (1 nm)/Al (100 nm)] that is fabricated by adopting TPE-DB as both the light emitter and electron transporter exhibits excellent electroluminescent performance, with high efficiencies of up to 13.5 cd A and 4.6%, which are advanced noticeably relative to those attained from the device with an additional electron-transporting layer (TPBi). The results demonstrate that these new TPE derivatives are promising n-type solid-state luminescent materials with practical utility in nondoped OLEDs.

Chen Long    Lin Gengwei    Peng Huiren    Han Nie    Zhuang Zeyan    Shen Pingchuan    Ding Siyang    Huang Dijie    胡蓉蓉    Shuming Chen    Fei Huang    Anjun Qin    Zujin Zhao    唐本忠    

Journal of Materials Chemistry C

2016

The research on aggregation-induced emission (AIE) has been a hot topic in the fields of photo-physics and luminescent materials. Design and synthesis of new AIE-active luminogens (AIEgens) will further promote the development of this area. Based on our developed new AIEgen of tetraphenylpyrazine (TPP), in this paper, we further enriched its family by covalently attaching thiophene unit on TPP core, and prepared three AIEgens of TPP-T, TPP-2T and T-TPP-T. Their structure-property relationship was studied in detail. The results showed that TPP-T, TPP-2T and T-TPP-T feature the aggregation-enhanced emission (AEE) characteristics. Their powders emit at 418, 437 and 436 nm with absolute fluorescence quantum yields of 26.8, 29.0 and 30.9%, respectively, which makes them promising to be used as emitting layer in fabrication of organic light-emitting diodes in combination with their excellent thermal stability.

Pan Lingxiang    Luo Wenwen    Chen Ming    Liu Junkai    Xu Lu    胡蓉蓉    Zujin Zhao    Anjun Qin    唐本忠    

Chinese Journal of Organic Chemistry

2016

A metal-free, multicomponent polymerization route for the facile construction of stereoregular functional polymers has been developed in this work. Boron trichloride-mediated polycoupling of terminal diynes and monoaldehydes was carried out in a stereoselective manner in dichloromethane under mild conditions and nitrogen, affording poly(dichloro pentadiene)s (PDPDs) with a predominant (E,Z)-configuration in high yields (up to 92%) with high molecular weights (M up to 174300) in several hours. All the polymers possessed good solubility in common organic solvents and showed high thermal stability, losing merely 5% of their weight at high temperatures of up to 384 °C. PDPDs carrying tetraphenylethylene (TPE) moieties exhibited a unique photophysical phenomenon of aggregation-induced emission (AIE): the emission of their weakly emissive solutions was turned on upon aggregation formation. Thin solid films of the polymers with good quality were readily fabricated on silica substrates by a simple spin-coating technique, and showed pretty high refractive indices (RI = 1.7937-1.4873) in a wide wavelength region of 400-890 nm. The PDPDs are photosensitive and such a property enables them to be promising materials for fabricating fluorescence patterns by the photolithography process.

Zhang Yun    Tseng Nai-Wen    Haiqin Deng    Ryan tsz kin Kwok    林荣业    唐本忠    

Polymer Chemistry

2016

Aggregation-induced emission (AIE) has become a hot topic for a variety of potential applications, but the understanding of its working mechanism is still under scrutiny. Herein, we proposed the use of the isotope effect (IE) to identify the AIE mechanism: under the restriction of an internal motion mechanism, the IE is pronouncedly different in excited-state decay rates when contrasting AIE luminogens (AIEgens) and non-AIEgens in theoretical calculations. For the complete deuteration of AIEgens, the IE of nonradiative decay rate in solution (<-10%) is much weaker than that (-65% to -95%) in aggregate, because the former stems from the overall results of competitive vibronic coupling and the severe mixing of low-frequency modes while the latter mainly comes from the vibronic coupling only. The experimental results confirm the isotopic "jump" behaviors in AIEgens well. However, non-AIEgens exhibit equivalent IEs (-40% to -90%) in both solution and solid phases. Further partial deuteration schemes for the 6-ring AIE analogues show positional dependence.

Zhang Tian    Qian Peng    Quan Changyun    Han Nie    Niu Yingli    Xie Yujun    Zujin Zhao    唐本忠     Zhigang Shuai   

Chemical Science

2016

We herein report a facile and efficient multicomponent click polymerization route to construct fused heterocyclic polymers with advanced functionalities. Mediated by CuI and trimethylamine at room temperature, diynes, disulfonyl azide, and salicylaldehyde, or o-hydroxylacetophenone undergo polymerizations efficiently and smoothly, affording high-molecular-weight poly(iminocoumarin)s (M up to 64 600) in satisfactory yields (up to 99%). This multicomponent click polymerization approach enjoys remarkable merits of both multicomponent reactions and click reactions, such as simple operation, high reaction efficiency and isolation yield, mild reaction conditions, and common substrates. The resulting polymers possess outstanding film-forming ability, high thermal stability, and good morphological stability. With tetraphenylethene luminogens embedded in the polymer chains, their solutions fluoresce weakly, whereas their aggregates emit intensely, demonstrative of a typical feature of aggregation-enhanced emission. Furthermore, the obtained polymers with bright film emission and high photosensitivity can be facilely fabricated into well-resolved 2D and 3D patterns by treatment of their films with UV light. Additionally, thanks to the highly polarized conjugated structures, the polymer films possess outstanding refractive indices (1.9284-1.7734) in the visible and near-IR regions (400-893 nm), which can be further adjusted by UV light.

Haiqin Deng    Ting Han    Engui Zhao    Ryan tsz kin Kwok    林荣业    唐本忠    

Macromolecules

2016