Heterocyclic polymers have gained enormous attention for their unique functionalities and wide applications. In contrast with the well-studied polymer systems with five- or six-membered heterocycles, functional polymers with readily openable small-ring heterocycles have rarely been explored due to their large synthetic difficulty. Herein, a facile one-pot multicomponent polymerization to such polymers is developed. A series of functional polymers with multisubstituted and heteroatom-rich azetidine frameworks are efficiently generated at room temperature in high atom economy from handy monomers. The four-membered azetidine rings in the polymer skeletons can be easily transformed into amide and amidine moieties via a fast and efficient acid-mediated ring-opening reaction, producing brand-new polymeric materials with distinctive properties. All the as-prepared azetidine-containing polymers exhibit intrinsic visible luminescence in the solid state under long-wavelength UV irradiation even without conventionally conjugated structures. Such unconventional luminescence is attributed to the clusteroluminogens formed by through-space electronic interactions of heteroatoms and phenyl rings. All the obtained polymers show excellent optical transparency, high and tunable refractive indices, low optical dispersions and good photopatternability, which make them promising materials in various advanced electronic and optoelectronic devices. The ring-opened polymers can also function as a lysosome-specific fluorescent probe in biological imaging.

Ting Han;Haiqin Deng;Zijie Qiu;Zheng Zhao;Haoke Zhang;Hang Zou;Nelson L.C. Leung;Guogang Shan;Mark R.J. Elsegood;Jacky W.Y. Lam;本忠 唐

Journal of the American Chemical Society

2018-4-25

Currently, the development of aggregation-induced emission (AIE) luminogens (AIEgens) has enabled us to “see” never before seen scenery. However, not all AIEgens exhibit the impressive emission efficiency in aggregated states. Moreover, the emission color of AIEgens can be seriously affected when their performance is improved. Therefore, to overcome this limitation, an efficient method is proposed here through the tailored alkyl linkages to greatly improve the emission efficiency of tetraphenylethene (TPE)-based AIEgens but retain their emission color. Encouragingly, significantly enhanced emission efficiency is achieved with the quantum yield up to 68.19% and 65.20% for BTPE-C4 and BTPE-C8, respectively, in contrast to that of TPE (25.32%), demonstrating the proverb that one plus one is much larger than two (1 + 1 >> 2). Interestingly, when alkyl linkages in skeletons are fine-tuned, self-assembled nanorods, nanosheets, and nanofibers are successfully achieved for BTPE-C1, BTPE-C4, and BTPE-C8 in tetrahydrofuran and water system. Also, these developed emissive AIEgens not only exhibit impressive response to the environmental stimuli of mechanical force, viscosity, temperature, and light, but can also be used to dynamically monitor and control the phase-separated morphology in polymeric blends.

Dongfeng Dang;Zijie Qiu;Ting Han;Yong Liu;Ming Chen;Ryan T.K. Kwok;Jacky W.Y. Lam;本忠 唐

Advanced Functional Materials

2018-4-18

Superior artificial light-harvesting systems (ALHSs) require exceptional capacity in harvesting light and transferring energy. In this work, we report a novel strategy to build ALHSs with an unprecedented antenna effect (35.9 in solution and 90.4 in solid film). The ALHSs made use of a conjugated polymeric supramolecular network (CPSN), a crosslinked network obtained from the self-assembly of a pillar[5]arene-based conjugated polymeric host (CPH) and conjugated ditopic guests (Gs). The excellent performance of the CPSN could be attributed to the following factors: 1) The “molecular wire effect” of the conjugated polymeric structure, 2) aggregation-induced enhanced emission (AEE) moieties in the CPH backbone, and 3) high capacity of donor–acceptor energy transfer, and 4) crosslinked structures triggered by the host–guest binding between Gs and CPH. Moreover, the emission of the CPSN could be tuned by using different Gs or varying the host/guest ratio, thus reaching a 96 % sRGB area.

Linxian Xu;Zaiyu Wang;Rongrong Wang;Lingyun Wang;Xuewen He;焕峰 江;Hao Tang;Derong Cao;本忠 唐

Angewandte Chemie - International Edition

2020-6-15

Since the discovery of the aggregation-induced emission (AIE) phenomenon in 2001, research on AIE molecules has drawn much attention, and this area has been expanding tremendously. This brief review will focus on recent advances in the science and application of AIE molecules, including new mechanistic understanding, new AIE molecules for sensing and imaging, stimuli-responsive AIE molecules and applications of AIE molecules for OLEDs. Moreover, this review will give a perspective on the possible opportunities and challenges that exist in the future for this area.

Yuancheng Wang;Guanxin Zhang;Meng Gao;Yuanjing Cai;Chi Zhan;Zujin Zhao;德清 张;本忠 唐

Faraday Discussions

2017

This book explores the aggregation-induced emission (AIE) effect, which has opened new avenues for the development of advanced luminogenic materials in the aggregate or solid state. By enabling light emission in the practically useful solid state, AIE has the potential to significantly expand the technological applications of luminescent materials. This book addresses principles, methods, and applications of AIEs, offering a new platform for the investigation of light-emitting processes from luminogen aggregates. Applications of AIE include biomedical diagnostics, sensor materials, and optoelectronic devices, among others, and are described in detail within the book. The development of a new generation of AIEgens, a deep understanding of the AIE mechanism(s), and the exploration of advanced technological applications will enable this exciting field to develop further. Headed by the pioneering researcher who started the field, Professor Ben Zhong Tang, this book combines both principles and applications and brings together global researchers in the field to report the progress, current challenges, and potential breakthroughs that may be accomplished in the near future.

Youhong Tang;本忠 唐

2018-10-9

A group of pyrene-containing poly(phenylacetylene)s (PPAs) with high molecular weight (M_w up to ∼ 170 000) were synthesized in high yields (up to ∼96%). Simply mixing the polymers and multiwalled carbon nanotubes (MWNTs) in an appropriate solvent afforded the polymer/MWNT hybrids with MWNT contents up to ∼25 wt %, which are soluble in common organic solvents such as chloroform and THF. The solubility can be as high as 637.5 mg/L in THF, thanks to the "additive effect" of the PPA skeleton and the pyrene pendants in solubilizing the MWNTs. The solubilization is realized through the spontaneous wrapping of the polymer chains round the MWNT shells, which is driving by the favorable π-π interactions of the PPA skeleton and the pyrene rings with the MWNT walls. The P2(5)/MWNT hybrid is thermally stable, losing little of its weight when heated to 338°C. The P2(m)/MWNT hybrids are electronically more conjugated and emit blue-green light more efficiently than their parent polymers upon photoexcitation. The surface photovoltaic cell fabricated from the P2(5)/MWNT hybrid is bipolar, suggesting an efficient photoinduced charge transfer between the two components, i.e., P2(5) and MWNT.

Wang Zhang Yuan;Jing Zhi Sun;Yongqiang Dong;Matthias Häussier;Feng Yang;Hai Peng Xu;Anjun Qin;Jacky W.Y. Lam;Qiang Zheng;本忠 唐

Macromolecules

2006-11-14

Organic microlasers have attracted much attention due to their unique features such as high mechanical flexibility, facile doping of gain materials, high optical quality, simplicity and low-cost fabrication. However, organic gain materials usually suffer from aggregation-caused quenching (ACQ), preventing further advances of organic microlasers. Here, a new type of microlaser from aggregation-induced emission (AIE) material is successfully demonstrated. By introducing a typical noncrystalline AIE material, a high quality microlaser is obtained via a surface tension-induced self-assembly approach. Distinct from conventional organic microlasers, the organic luminescent material used here is initially nonluminescent but can shine after aggregation under optical pumping. Further investigations demonstrate that AIE-based microlasers exhibit advantages to enable much higher doping concentrations, which provides an alternative way to improved lasing performance including dramatically reduced threshold and favorable lasing stability. It is believed that these results could provide a promising way to extend the content of microlasers and open a new avenue to enable applications ranging from chemical sensing to biology.

Wangwang Liu;Huakang Yu;Rongrong Hu;Tao Xu;Yipeng Lun;Jiulin Gan;Shanhui Xu;Zhongmin Yang;本忠 唐

Small

2020-2-1

Full conjugated multilayer thin films fabricated by the alternate adsorption of partially doped polyaniline (PANI) as a polycation and water-soluble poly (4-carboxyphenyl) acetylene (PA) as a polyanion were used as nanoreactors to study the in situ preparation of PbS nanoparticles. First, the self-assembled multilayers were immersed in a 1 mol/L NaOH solution to fabricate a controlled content of free carboxylic acid binding groups. Chemical reaction within the polymer film was initiated by absorbing Pb²⁺ from a 0.4 mol/L aqueous solution of Pb(Ac)₂ and followed by exposing the film to H₂S gas. UV-Vis absorption studies reveal that the absorption spectral profiles of the films are dependent on the dipping time of the film in the Pb (Ac)₂ solution. AFM and TEM microscopic examinations of the films reveal that PbS crystals with rhomboid structures are formed in the films. The particles of narrow size distribution stand vertically on the film plane. Due to being doped by PbS, the photoelectric conversion property of ultra-thin composite films, which can be measured with a conventional three-electrode photoelectrochemical cell using 0.5 mol/L KCl solution as the supporting electrolyte, is improved obviously. The results show that the value of the photocurrent for an 8-layer film is 3 times higher than that of the original film.

Lingling Gao;Bin Tong;Guijun Yao;Yuping Dong;Maofeng Zhang;Jacky Wing Yip Lam;本忠 唐

Acta Polymerica Sinica

2005-6

To improve the treatment efficiency and reduce side effects in cancer therapy, accurate diagnosis of cancer cell types at a molecular level is highly desirable. Fluorescent nanoparticles (NPs) are especially suitable for detecting molecular biomarkers of cancer with advantages of superior brightness, easy decoration and high resolution. However, the conventional organic fluorophores, conjugated polymers, and inorganic quantum dots suffer from the drawbacks of aggregation-caused quenching (ACQ), low photostability, and heavy metal toxicity, respectively, which severely restrict their applications in NPs-based fluorescence imaging. To overcome these limitations, herein, we have developed fluorescent nanoparticles based on a t-BuPITBT-TPE fluorophore derived from aggregation-induced emission (AIE)-active tetraphenylethene. Through encapsulating t-BuPITBT-TPE within biocompatible DSPE-PEG and further decorating with a monoclonal antibody cetuximab (C225), the obtained t-BuPITBT-TPE-C225 NPs can be used for targeted imaging of non-small cell lung cancer cells with an overexpressed epidermal growth factor receptor (EGFR). The specific targeting ability of t-BuPITBT-TPE-C225 NPs has been well verified by confocal microscopy and flow cytometry experiments. The t-BuPITBT-TPE-C225 NPs have shown significant advantages in terms of highly efficient red emission, good bio-compatibility, and excellent photostability. This work provides a promising method for precise diagnosis of cancer cells by antibody-functionalized fluorescent NPs with high brightness.

Meng Gao;Huifang Su;Gengwei Lin;Shiwu Li;Xingsu Yu;Anjun Qin;Zujin Zhao;Zhenfeng Zhang;本忠 唐

Nanoscale

2016-8-28

Fixing carbon dioxide (CO₂) into useful polymeric materials has attracted broad interest since carbon dioxide is an abundant, inexpensive, nontoxic, and renewable C1 resource. Nevertheless, the polymerization of CO₂ and alkynes attracted less attention because the propagation step involving CO₂ is a major obstacle. Herein, we overcome this obstacle by developing a facile and efficient Ag₂WO₄-catalyzed polymerization of CO₂, diynes, and alkyl dihalides under mild reaction conditions. Soluble and thermally stable poly(alkynoate)s with high weight-average molecular weights (up to 31 400) were obtained in high yields (up to 95%). Thanks to its unique reaction mechanism, this step-growth polymerization can produce an ethynyl group terminated telechelic polymer that can be used as macromonomer to prepare poly(alkynoate)s with higher molecular weights by either continually adding alkyl dihalide into the reaction solution or mixing the isolated telechelic polymers with alkyl dihalide and catalytic system under a CO₂ atmosphere. The resultant polymers show versatile properties. The tetraphenylethene, silole, and tetraphenylpyrazine moieties that feature the aggregation-induced emission (AIE) characteristics can be facilely incorporated into the polymer main chains to make them AIE active with high absolute quantum yields up to 61% in the film state. Their containing ester linkages endow the polymers degradable under basic conditions, and the alkynoate repeating units enable them to be postfunctionalized by the powerful amino-yne click reaction to generate nitrogen-containing stereo- and regioregular polymers with unity grafting ratio. Thus, this work not only establishes a powerful polymerization to directly fix CO₂ but also provides poly(alkynoate)s with versatile properties.

Bo Song;Benzhao He;Anjun Qin;本忠 唐

Macromolecules

2018-1-9