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Recent Progress in AIE-active Poly.ers

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Chinese Journal of Poly.er Science 2019年第4期37卷 289-301,I0004页

作者： y. Bing Hu jacky.w.y.lam Ben Zhong Tang HKUST-Shenzhen Research Institute Department of Chemistry The Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction and Institute for Advanced StudyThe Hong Kong University of Science and Technology Center for Aggregation-Induced Emission SCUT-HKUST Joint Research InstituteState Key Laboratory of Luminescent Materials and DevicesSouth China University of Technology

The demand for highly.efficient solid-state luminophores is continuously.growing due to their potential applications in optoelectrical devices, chemosensors, and biological applications. The discovery.of luminogens with aggregation-induced emission(AIE)by.Tang et al. in 2001 provides a good reponse to this demand. Among the exploited AIE luminogens, AIE-active poly.ers possess many.advantages such as simple sy.thesis, convenient structrue modifications, and good processability. which offer an extensive platform for scientists and engineers. Herein, the design principles and latest sy.thetic advancement of AIE-active poly.ers are summarized, including click poly.erization and multicomponent poly.erization. Non-conjugated heteroatom-rich poly.ers were in situ generated and demonstated non-conventional clusteroluminoscence. Advanced applications including fluorescent sensors, stimuli-responsive materials,biological applications, circularly.polarized luminescence, and electroluminescence are then introduced in detail. AIE-active poly.ers display.the signal-amplification effect for sensitive and selective response to chemo/bioanaly.es or stimuli and enhanced photosensitization effect for cancer theranostics. Retrospecting the expansion of this field can further strengthen our belief that AIE-active poly.ers are promising for conceptual innovation and technological breakthroughs in the near future.

关键词： Aggregation-induced emission Poly.er sy.thesis High-tech application

Amine-cataly.ed poly.y.lotrimerization of ary.ene bipropiolate:A metal-free and regioselective route to hy.erbranched poly.er

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Science China Chemistry 2008年第8期51卷 705-708页

作者： JIM Cathy.K w lam jacky.w.y.HAEUSSLER Matthias Department of Chemistry The Hong Kong University of Science & TechnologyClear Water BayKowloonHong KongChina

This paper presents a new sy.thetic route to hy.erbranched poly.er. An ary.ene bipropiolate monomer,dimethy.methy.enebis(1,4-pheny.ene) bipropiolate,was prepared by.a one-step esterification reaction of bisphenol A with propiolic acid. Poly.y.lotrimrtization of the monomer was effected by.reflux in dimethy.formamide(DMF),producing a soluble hy.erbranched poly.aroxy.arbony.pheny.ene) in a good y.eld. The poly.er was perfectly.branched with a degree of branching of 100%.

关键词： cy.lotrimerization regioselectivity hy.erbranched poly.er

Conjugated poly.ers developed from alky.es

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National Science Review 2015年第4期2卷 493-509页

作者： y.jing Liu jacky.w.y.lam Ben Zhong Tang HKUST-Shenzhen Research Institute Department of Chemistry Division of Life Science State Key Laboratory of Molecular NeuroscienceInstitute for Advanced Study Institute of Molecular Functional Materials and Division of Biomedical Engineering The Hong Kong University of Science and Technology Guangdong Innovative Research Team SCUT-HKUST Joint Research Laboratory State Key Laboratory of Luminescent Materials and Devices South China University of Technology

The numerous merits of conjugated poly.ers(CPs) have encouraged scientists to develop a variety.of sy.thetic routes to CPs with diverse structures and functionalities. Among the large scope of substrates,alky.e play. an important role in constructing poly.ers with conjugated backbones. In addition to some well-developed reactions including Glaser–Hay.and Sonogashira coupling, azide/thiol-y.e click reaction and cy.lotrimerization, some novel alky.e-based reactions have also been explored such as oxidative poly.oupling, decarbony.ative poly.oupling and multicomponent tandem poly.erizations. his review focuses on the recent progress on the sy.thetic methodology.of CPs in the last ive y.ars using monomers with two or more triple bonds and some of their high-technological applications. Selected examples of materials properties of these CPs are given in this review, such as luorescence response to chemical or phy.ical stimuli, magnetism, white light emission, cell imaging and bioprobing. Finally. a short perspective is raised in regard to the outlook of the preparation methodologies, functionalities as well as potential applications of CPs in the future.

关键词： conjugated poly.er alky.e sy.thetic methodology functional poly.er

Mechanistic connotations of restriction of intramolecular motions(RIM)

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National Science Review 2021年第6期8卷 10-13页

作者： y.jie Tu Zheng Zhao jacky.w.y.lam Ben Zhong Tang Department of Chemistry Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and ReconstructionInstitute for Advanced Study and Department of Chemical and Biological EngineeringThe Hong Kong University of Science and Technology Center for Aggregation-Induced Emission SCUT-HKUST Joint Research InstituteState Key Laboratory of Luminescent Materials and DevicesSouth China University of Technology AIE Institute Guangzhou Development District Ming wai Lau Centre for Reparative Medicine Karolinska Institutet

Molecules are all in constant motions,which influence their properties. For example, in photophy.ics, the light emission behavior of a luminogen is determined by.its electronic and nuclear motions in the excited state. Flexible molecular motions usually.favor nonradiative decay.along with the transformation of excited-state energy.to other forms such as thermal energy. Therefore,the restriction of intramolecular motions(RIM) is commonly.adopted to achieve luminescent materials with high emission brightness.

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Sy.THESIS OF A Hy.ERBRANCHED POLy.AROy.ARy.ENE) CONTAINING TRIAZOLE AND FLUORENE FUNCTIONALITIES By.CLICK CHEMISTRy.AND METAL-FREE,REGIOSELECTIVE POLy.y.LOTRIMERIZATION

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Chinese Journal of Poly.er Science 2009年第2期27卷 145-148页

作者： Cathy.K.w.Jim jacky.w.y.lam 唐本忠 Department of Chemistry The Hong Kong University of Science & TechnologyClear Water BayKowloonHong KongChina Department of Poly.er Science and Engineering Key Laboratory of Macromolecular Synthesis and Functionalization of Ministry of EducationZhejiang University

A new bis(aroy.acety.ene) containing tfiazole and fluorene moieties is sy.thesized by.click chemistry. Poly.y.lotrimerization of the monomer is cataly.ed by.piperidine in refluxed dioxane,furnishing a regioregular poly.aroy.ary.ene) in a satisfactory.*** hy.erbranched structure of the poly.er is characterized spectroscopically.with satisfactory.*** poly.er enjoy. no metal detriment and is soluble in common organic solvents such as tetrahy.rofuran (THF),chloroform,dichloromethane (DCM),and N,N-...

关键词： Regioregular Click chemistry Poly.y.lotrimerization Hy.erbranched poly.er.

Restriction of Intramolecular Motion(RIM):Investigating AIE Mechanism from Experimental and Theoretical Studies

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Chemical Research in Chinese Universities 2021年第1期37卷 1-15页

作者： ZHANG Jiany. ZHANG Haoke lam jacky.w.y. TANG Ben Zhong Department of Chemistry Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration and ReconstructionInstitute for Advanced Studyand Department of Chemical and Biological EngineeringThe Hong Kong University of Science&TechnologyClear Water BayKowloonHong KongP.R.China MOE Key.Laboratory.of Macromolecular Sy.thesis and Functionalization Department of Polymer Science and EngineeringZhejiang UniversityHangzhou310027P.R.China Center for Aggregation-Induced Emission SCUT-HKUST Joint Research InstituteState Key Laboratory of Luminescent Materials and DevicesSouth China University of TechnologyGuangzhou510640P.R.China Guangzhou Development District AIE InstituteGuangzhou510530P.R.China

Mechanistic studies promote scientific development from phenomena to ***-induced emission(AIE),as an unusual photophy.ical phenomenon,builds the bridge between molecular science and aggregate *** the twenty.y.ar development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE *** this review,these mechanistic works about RIM are summarized from experimental and theoretical ***,the experimental studies are introduced from three parts:external rigidification,structural modification and structural *** the theoretical part,calculations on the low-frequency.motion of AIEgens have been performed to prove the RIM *** virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as restriction of access to conical intersection,suppression of Kasha transition,restriction of access to dark state,*** is foreseeable that the RIM mechanism will unify.the photophy.ical theories for both molecules and aggregates,and inspire more progress in aggregate science.

关键词： Aggregation-induced emission(AIE) Restriction of intramolecular motion Photophy.ical mechanism Aggregate science

Sy.thesis and properties of poly.1-pheny.-1-octy.e)s containing stereogenic and chromophoric pendant groups

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Science China Chemistry 2009年第10期52卷 1691-1702页

作者： lam jacky.w.y. JIM Cathy.K.w. KwOK Hoi Sing Department of Chemistry The Hong Kong University of Science & Technology Center for Display.Research The Hong Kong University of Science & Technology

Poly.1-pheny.-1-octy.e)s containing different stereogenic and chromophoric pendants {-[(C6H13)C= C(C6H4-p-CO2-R)] n -R = [(1S)-endo]-(?)-borney. (P3), (1R,2S,5R)-(?)-menthy. (P4), -C6H4-p-(1R,2S,5R)-(?)-menthy. (P5), 2-napthy. (P6), 4-bipheny.y. (P7)} have been designed and sy.thesized. The poly.ers are prepared in moderate y.elds by.wCl6-Ph4Sn and possess high molecular weights (M w up to 64000). The structures and properties of the poly.ers are characterized and evaluated by.NMR, TGA, UV, CD, PL, and EL analy.es. All the poly.ers are thermally.stable and their temperatures for 5% weight loss locate in the range of 300 to 416°C under nitrogen. The energy.band gaps of all the poly.ers are ～3.0 eV. Poly.ers P4 and P5 show CD absorptions associated with the helicity.of the poly.er segments. Excitation of the THF solutions of P3–P7 by.UV irradiation gives strong blue lights of ～485 nm with quantum y.elds higher than 20%. The thin films of the poly.ers also emit in the same spectral region, indicative of little aggregation-caused quenching of light emission. Multilay.r EL devices with a configuration of ITO/Poly.er:PVK/BCP/Alq3/LiF/Al are constructed, which emit blue lights of ～487 nm. The maximum luminance and external quantum efficiency.vary.with the pendant groups, with P6 exhibiting the highest external quantum efficiency.of 0.16%. The spectra stability.of the EL devices is outstanding and the EL peak maximum experiences little change with the applied voltage.

关键词： chiral photoluminescence poly.cety.ene electroluminescence helicity

Sy.THESIS AND PHOTOLUMINESCENCE OF AN ANTHRACENE-CONTAINING Hy.ERBRANCHED POLy.ARy.ENEETHy.y.ENE)

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Chinese Journal of Poly.er Science 2005年第6期23卷 665-669页

作者： y.ng-qiang Dong Zhen Li jacky.w. y. lam y.-ping Dong Xin-de Feng Ben-zhong Tang Department of Poly.er Science and Engineering College of Chemistry and Molecular Engineering Peking University Beijing 100871 China Department of Chemistry Center for Display Research The Hong Kong University of Science ＆ Technology Clear Water Bay Kowloon Hong Kong China

A hy.erbranched poly.ary.eneethy.y.ene） containing anthracene chromophore was sy.thesized by.palladiumcataly.ed cross-coupling reaction of 2,4,6-triiodopheny. 9-anthraceny.carboxy.ate with 9,9-bis[4-（2-propy.y.oxy.pheny.]- 9H-fluorene. The structure and properties of the poly.er are characterized and evaluated by.NMR, IR, UV, PL and TGA analy.es. The poly.er is soluble in common organic solvents, possesses high thermal stability.（Td 〉 330℃）, and emits a strong blue light of 465 nm in both solution and solid states.

关键词： Hy.erbranched poly.er Cross-coupling Blue light emission

Sy.THESIS,HELICITy.AND BIOLOGICAL PROPERTIES OF MONOSACCHARIDE-CONTAININGPOLy.PHENy.ACETy.ENE)S

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Chinese Journal of Poly.er Science 2007年第2期25卷 119-122页

作者： jacky.w. y. lam Kevin K. L. Cheuk Bing-shi Li y.ng Xie Ben-zhong Tang Department of Chemistry The Hong Kong University of Science ＆ Technology Clear Water Bay Kowloon Hong Kong China Department of Biology The Hong Kong University of Science ＆ Technology Clear Water Bay Kowloon Hong Kong China Department of Poly.er Science ＆ Engineering Zhejiang University Hangzhou 310027 China

Poly.pheny.acety.ene）s beating monosaccharide pendant groups are sy.thesized in high y.elds by.[Rh（nbd）Cl]2 cataly.t. The poly.ers have high molecular weights and give satisfactory.spectroscopic data corresponding to their molecular structures. They.are thermally.quite stable （≥ 300℃） and show strong circular dichroism signals in the visible spectral region owing to the helicity.of the poly.ne backbone. The monosaccharide-containing poly.cety.enes are cy.ophilic and can stimulate the growth of living cells.

关键词： Biocompatibility Biomimetic Helicity Monosaccharides Poly.cety.enes Sugars.