The development of new polymerization routes to afford N-heterocyclic polymers is of vital importance and highly desired for various practical applications. Herein, a facile and efficient polyannulation reaction of du...The development of new polymerization routes to afford N-heterocyclic polymers is of vital importance and highly desired for various practical applications. Herein, a facile and efficient polyannulation reaction of dual-activated alkyne and pyridines was developed to construct novel N-heterocyclic poly(quinolizine)s. This polymerization can proceed smoothly under catalystfree conditions with 100% atom utilization to furnish poly(quinolizine)s with high molecular weights(up to 34,100) and welldefined structures in acceptable yields. The resulting polymers show good solubility, high thermal stability and strong red emission. Moreover, the prepared poly(quinolizine)s exhibit low cytotoxicity and can selectively label lysosomes in live cells.Considering the remarkable advantages of readily available raw materials, mild polymerization conditions, atom economy, and excellent product performance, this new and efficient polymerization tool will open up enormous opportunities for preparing functional N-heterocyclic polymers.展开更多
The development of new and efficient polymerization strategies for the synthesis of multisubstituted fused heterocyclic polymers with attractive properties is of great significance.Herein,a rhodium-catalyzed polyannul...The development of new and efficient polymerization strategies for the synthesis of multisubstituted fused heterocyclic polymers with attractive properties is of great significance.Herein,a rhodium-catalyzed polyannulation route is developed for the in situ generation of multisubstituted polyquinolines with efficient aggregate-state fluorescence.Based on the cascade C-H activation of isonicotinamides and their annulations with internal diynes,a series of high molecular weight polyquinolines are efficiently produced in high yields of up to 99%in a facile and atom-economical manner.Unlike conventional two-component stepwise polymerizations,these polyannulation reactions are tolerant to monomer non-stoichiometric conditions and proceed even more thoroughly in the presence of an excess amount of the isonicotinamide monomer.Benefiting from the unique multisubstituted polyquinoline structures,the obtained polymers show high thermal and morphological stability,useful aggregation-induced emission(AIE)properties,and tunable aggregated-state fluorescence behaviors.The AIE-active polyquinoline is demonstrated to be a good lysosome-specific fluorescent probe with low cytotoxicity and excellent photostability.展开更多
The development of C-H activation-based polymerization strategies for the facile and efficient construction of novel functional fused heterocyclic polymers is an important but challenging task.Herein,we report a facil...The development of C-H activation-based polymerization strategies for the facile and efficient construction of novel functional fused heterocyclic polymers is an important but challenging task.Herein,we report a facile and atom-economical C-H activation/annulation polymerization(CAAP)approach that enables the in-situ formation of unique diheterocycle-fused polymers from readily available monomers based on the C-H activation of olefins.The rhodium-catalyzed polymerizations of fumaric acid and internal diynes proceed smoothly under mild conditions,producing a series of multisubstituted poly(dilactone)s with high molecular weights(M_(w)up to 109,600)in moderate to high yields of up to 98.4%.The presence of multiple aryl substituents around the dilactone units endows the resulting polymers with good solution processibility and readily tunable fluorescent properties.Most of the synthesized poly(dilactone)s exhibit aggregation-induced emission(AIE)properties,showing efficient aggregate-state fluorescence.The AIE-active poly(dilactone)can function as a good lysosome-specific fluorescent probe in biological imaging with low cytotoxicity.It is anticipated that these straightforward and economic CAAP reactions together with the structure-property relationship study in this work could promote the exploration of fused heterocyclic polymer materials with more diversified structures and advanced functionalities.展开更多
基金supported by the National Natural Science Foundation of China(22101028,21788102)the start-up funding from Beijing Normal University(310432102,310432103)+3 种基金the Innovation and Technology Commission(ITC-CNERC14SC01)the Science and Technology Plan of Shenzhen(JCYJ20160229205601482,JCYJ20180507183832744,JCYJ20170818113602462)the Natural Science Foundation of Guangdong Province(2019B121205002)the Research Grants Council of Hong Kong(16305618,16304819,16305320,NHKUST609/19,C6009-17G,C6014-20W/16)。
文摘The development of new polymerization routes to afford N-heterocyclic polymers is of vital importance and highly desired for various practical applications. Herein, a facile and efficient polyannulation reaction of dual-activated alkyne and pyridines was developed to construct novel N-heterocyclic poly(quinolizine)s. This polymerization can proceed smoothly under catalystfree conditions with 100% atom utilization to furnish poly(quinolizine)s with high molecular weights(up to 34,100) and welldefined structures in acceptable yields. The resulting polymers show good solubility, high thermal stability and strong red emission. Moreover, the prepared poly(quinolizine)s exhibit low cytotoxicity and can selectively label lysosomes in live cells.Considering the remarkable advantages of readily available raw materials, mild polymerization conditions, atom economy, and excellent product performance, this new and efficient polymerization tool will open up enormous opportunities for preparing functional N-heterocyclic polymers.
基金supported by the National Natural Science Foundation of China(22271197,21905176)the Natural Science Foundation for Distinguished Young Scholars of Guangdong Province(2020B1515020011)+1 种基金the Science and Technology Plan of Shenzhen(JCYJ20190808142403590,JCYJ20190808153415062)the Instrumental Analysis Center of Shenzhen University。
文摘The development of new and efficient polymerization strategies for the synthesis of multisubstituted fused heterocyclic polymers with attractive properties is of great significance.Herein,a rhodium-catalyzed polyannulation route is developed for the in situ generation of multisubstituted polyquinolines with efficient aggregate-state fluorescence.Based on the cascade C-H activation of isonicotinamides and their annulations with internal diynes,a series of high molecular weight polyquinolines are efficiently produced in high yields of up to 99%in a facile and atom-economical manner.Unlike conventional two-component stepwise polymerizations,these polyannulation reactions are tolerant to monomer non-stoichiometric conditions and proceed even more thoroughly in the presence of an excess amount of the isonicotinamide monomer.Benefiting from the unique multisubstituted polyquinoline structures,the obtained polymers show high thermal and morphological stability,useful aggregation-induced emission(AIE)properties,and tunable aggregated-state fluorescence behaviors.The AIE-active polyquinoline is demonstrated to be a good lysosome-specific fluorescent probe with low cytotoxicity and excellent photostability.
基金supported by the National Natural Science Foundation of China(22271197)the Guangdong Basic and Applied Basic Research Foundation(2025B1515020021,2023A15150-11578)+3 种基金the Shenzhen Science and Technology Program(RCYX20221008092924059,JCYJ20220531102601003)the Key-Area Research and Development Program of Guangdong Province(2024B0101040001)the 2035 Research Excellence Program of Shenzhen University(2023C001)the Instrumental Analysis Center of Shenzhen University for the support。
文摘The development of C-H activation-based polymerization strategies for the facile and efficient construction of novel functional fused heterocyclic polymers is an important but challenging task.Herein,we report a facile and atom-economical C-H activation/annulation polymerization(CAAP)approach that enables the in-situ formation of unique diheterocycle-fused polymers from readily available monomers based on the C-H activation of olefins.The rhodium-catalyzed polymerizations of fumaric acid and internal diynes proceed smoothly under mild conditions,producing a series of multisubstituted poly(dilactone)s with high molecular weights(M_(w)up to 109,600)in moderate to high yields of up to 98.4%.The presence of multiple aryl substituents around the dilactone units endows the resulting polymers with good solution processibility and readily tunable fluorescent properties.Most of the synthesized poly(dilactone)s exhibit aggregation-induced emission(AIE)properties,showing efficient aggregate-state fluorescence.The AIE-active poly(dilactone)can function as a good lysosome-specific fluorescent probe in biological imaging with low cytotoxicity.It is anticipated that these straightforward and economic CAAP reactions together with the structure-property relationship study in this work could promote the exploration of fused heterocyclic polymer materials with more diversified structures and advanced functionalities.
