Inspired by the highly efficient and enantioselective reactions catalyzed by biomacromolecules, developing artificial helical polymer-supported catalysts is an attractive and meaningful field. In this work, a series of helical polymers poly-1ns with controlled molecular mass (Mns) and narrow molecular mass distribution (Mw/Mns) bearing cinchona alkaloid pendants was obtained by asymmetric polymerization of corresponding monomer. The poly-1ns exhibited intense positive Cotton effect at 364 nm, indicating preferred righted-handed helix was formed in their backbone. Due to the catalytic groups on pendants and helix in the backbone, poly-1ns exhibited satisfied catalytic efficiency on asymmetric Henry reaction. Compared to small molecule (1) with similar structures, enantioselectivity of Henry reaction was significantly enhanced using poly-1n as catalyst. The enantiomeric excess (ee) value of the Henry reaction could be up to 75%. Furthermore, the helical polyisocyanide catalyst could be recovered and reused facilely at least five cycles without apparent significant loss of its enantioselectivity.
{"title":"Optically active helical polymers bearing cinchona alkaloid pendants: an efficient chiral organocatalyst for asymmetric Henry reaction","authors":"Xing-Yu Zhou, Wen-Gang Huang, Xue-Cheng Sun, Hui Zou, Li Zhou, Zong-Quan Wu","doi":"10.1039/d4py01284d","DOIUrl":"https://doi.org/10.1039/d4py01284d","url":null,"abstract":"Inspired by the highly efficient and enantioselective reactions catalyzed by biomacromolecules, developing artificial helical polymer-supported catalysts is an attractive and meaningful field. In this work, a series of helical polymers poly-1ns with controlled molecular mass (Mns) and narrow molecular mass distribution (Mw/Mns) bearing cinchona alkaloid pendants was obtained by asymmetric polymerization of corresponding monomer. The poly-1ns exhibited intense positive Cotton effect at 364 nm, indicating preferred righted-handed helix was formed in their backbone. Due to the catalytic groups on pendants and helix in the backbone, poly-1ns exhibited satisfied catalytic efficiency on asymmetric Henry reaction. Compared to small molecule (1) with similar structures, enantioselectivity of Henry reaction was significantly enhanced using poly-1n as catalyst. The enantiomeric excess (ee) value of the Henry reaction could be up to 75%. Furthermore, the helical polyisocyanide catalyst could be recovered and reused facilely at least five cycles without apparent significant loss of its enantioselectivity.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qiqi Dai, Yao Long, Xupeng Han, Yang Yang, Yi Yang, Yawen Fu, Wenjun Yi, Xiaoxing Gu, Kun Liu, Lijun Li
Polydiene-basedliquid rubber can be used to prepare high frequency copper-clad plates, and is also the most critical raw material for photosensitive elastomers for flexible resin plates. The molecular structure control requirements of high-performance liquid rubber are very high, and special living anionic initiation systems and polymerization processes need to be found to achieve stable control of product structure. In this paper, a series of novel polar modifiers were synthesized by introducing alkyl substituents and N/O-containing heteroatoms into the cycloamine ring (1,2-dipiperidinoethane (DPE) derivatives), and the high vinyl polybutadiene (90% < 1,2-units < 99%) with quantitatively tertiary-amine functionalization (0% ~ 25% molar ratio) was synthesized by in-situ copolymerization using 4-dimethylaminomethylstyrene (VBA) as comonomer. The polymerization process has obvious characteristics of controllable and living under mild conditions. The fine structure of the product was analyzed by 1HNMR, FTIR, GPC and DSC. In situ anionic copolymerization provides a new way to develop high-performance liquid rubber.
{"title":"Facile Synthesis of Functionalized High Vinyl Polybutadiene by Using 1,2-Dipiperidinoethane Derivatives as Polar Modifier","authors":"Qiqi Dai, Yao Long, Xupeng Han, Yang Yang, Yi Yang, Yawen Fu, Wenjun Yi, Xiaoxing Gu, Kun Liu, Lijun Li","doi":"10.1039/d5py00227c","DOIUrl":"https://doi.org/10.1039/d5py00227c","url":null,"abstract":"Polydiene-basedliquid rubber can be used to prepare high frequency copper-clad plates, and is also the most critical raw material for photosensitive elastomers for flexible resin plates. The molecular structure control requirements of high-performance liquid rubber are very high, and special living anionic initiation systems and polymerization processes need to be found to achieve stable control of product structure. In this paper, a series of novel polar modifiers were synthesized by introducing alkyl substituents and N/O-containing heteroatoms into the cycloamine ring (1,2-dipiperidinoethane (DPE) derivatives), and the high vinyl polybutadiene (90% < 1,2-units < 99%) with quantitatively tertiary-amine functionalization (0% ~ 25% molar ratio) was synthesized by in-situ copolymerization using 4-dimethylaminomethylstyrene (VBA) as comonomer. The polymerization process has obvious characteristics of controllable and living under mild conditions. The fine structure of the product was analyzed by 1HNMR, FTIR, GPC and DSC. In situ anionic copolymerization provides a new way to develop high-performance liquid rubber.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Understanding how chemical reaction mechanisms prescribe network architecture and the resulting properties is key to applications across fields. Herein we report photo-dose tunable crosslinking density in fully formed polymer networks by exploiting the relative rates of thiol-ene click chemistry and chain-growth homopolymerization in symmetric triene monomers. Synthesized via one-step functionalization of biomass-derived diacids, these trienes incorporate terminal allyl ether groups and internal fumarate/maleate groups for varying reactivity. Through small-molecule addition with monothiol, 1H-NMR results indicate fast preferential thiol addition to terminal allyl groups and slower stereochemistry-dependent homopolymerization of fumarate/maleate groups. Incorporating these monomers with dithiol and triallyl crosslinker allowed formation of polymer networks, using both thiol-ene addition and homopolymerization as photo-crosslinking mechanisms on differing timescales. In-situ photorheology and dynamic mechanical analysis demonstrate impacts of the mixed-mechanism on light-dependent evolution of network architecture from initial gelation to increasing crosslinking density with prolonged exposure. Ultimately, the mixed-mechanism polymerization enables grayscale patterning and 3D printing, offering potential for in situ patterning of glassy and rubbery regions in monolithic materials.
{"title":"Harnessing Ene Type and Stereochemistry to Control Reaction Kinetics and Network Architecture in Thiol-Ene Photopolymerization Using Maleate and Fumarate–Derived Monomers","authors":"Rithwik Ghanta, Ayaulym Abilova, Cade McAndrew, Alexa Simone Kuenstler","doi":"10.1039/d4py01361a","DOIUrl":"https://doi.org/10.1039/d4py01361a","url":null,"abstract":"Understanding how chemical reaction mechanisms prescribe network architecture and the resulting properties is key to applications across fields. Herein we report photo-dose tunable crosslinking density in fully formed polymer networks by exploiting the relative rates of thiol-ene click chemistry and chain-growth homopolymerization in symmetric triene monomers. Synthesized via one-step functionalization of biomass-derived diacids, these trienes incorporate terminal allyl ether groups and internal fumarate/maleate groups for varying reactivity. Through small-molecule addition with monothiol, 1H-NMR results indicate fast preferential thiol addition to terminal allyl groups and slower stereochemistry-dependent homopolymerization of fumarate/maleate groups. Incorporating these monomers with dithiol and triallyl crosslinker allowed formation of polymer networks, using both thiol-ene addition and homopolymerization as photo-crosslinking mechanisms on differing timescales. In-situ photorheology and dynamic mechanical analysis demonstrate impacts of the mixed-mechanism on light-dependent evolution of network architecture from initial gelation to increasing crosslinking density with prolonged exposure. Ultimately, the mixed-mechanism polymerization enables grayscale patterning and 3D printing, offering potential for in situ patterning of glassy and rubbery regions in monolithic materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"43 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daniel Döpping, Felix H. Schacher, Andreas Stihl, Dominik Voll, Patrick Theato
Various poly(methyl methacrylate) (PMMA) and poly(acrylonitrile) (PAN) coated silica nanoparticles were synthesized via chain transfer polymerization with the goal to assess the coating behavior and characterization of polymer coated silica nanoparticles with monomers of different reactivities. The particles were characterized by thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM) and correlated to the free PMMA/PAN formed in the crude reaction mixture characterized with size exclusion chromatography (SEC). It was found that the mass loss observed in TGA and coating thickness obtained from TEM micrographs correlate strongly with the average polymer chain-length in the crude reaction mixture.
{"title":"Revisiting Polymer Coatings on Nanoparticles: Correlation between Molecular Weight and Coating Thickness in Chain Transfer Polymerizations","authors":"Daniel Döpping, Felix H. Schacher, Andreas Stihl, Dominik Voll, Patrick Theato","doi":"10.1039/d5py00081e","DOIUrl":"https://doi.org/10.1039/d5py00081e","url":null,"abstract":"Various poly(methyl methacrylate) (PMMA) and poly(acrylonitrile) (PAN) coated silica nanoparticles were synthesized via chain transfer polymerization with the goal to assess the coating behavior and characterization of polymer coated silica nanoparticles with monomers of different reactivities. The particles were characterized by thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM) and correlated to the free PMMA/PAN formed in the crude reaction mixture characterized with size exclusion chromatography (SEC). It was found that the mass loss observed in TGA and coating thickness obtained from TEM micrographs correlate strongly with the average polymer chain-length in the crude reaction mixture.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chuanqi Zhao, Hannah Schnicke, J. Diego Garcia-Hernandez, Jiandong Cai, Yifan Zhang, Charlotte E. Boott, Ian Manners
Two-dimensional (2D) nanoparticles have received considerable attention due to their versatile applications ranging from catalysis, optoelectronics to nanomedicine. However, it remains challenging to access size tunable flat nanostructures with spatially tailored chemistries. The seeded-growth method, “living” crystallization-driven self-assembly (CDSA) has emerged as a promising approach for preparing well-defined 1D and 2D core–shell micellar assemblies from crystallizable block copolymers (BCPs). Nevertheless, the development of biocompatible aliphatic polycarbonates, such as poly(trimethylene carbonate) (PTMC), as core-forming blocks for CDSA is considerably less explored and represents a key challenge due to their low crystallinity. Herein, we report the development of poly(dimethyltrimethylene carbonate) (PDTC) as a crystallizable core-forming block through the introduction of side chains to PTMC. The BCPs containing crystallizable PDTC were shown to undergo living CDSA to prepare uniform and size-controlled 2D platelets. In addition, uniform segmented platelets with spatially localized coronal chemistries were successfully constructed. The colloidal stability of the platelets in aqueous solution allowed for an assessment of their toxicity toward healthy WI-38 and cancerous U-87 MG cells. These studies reveal that PDTC nanostructures exhibit no discernible cytotoxicity and excellent biocompatibility, indicating great potential for biomedical applications.
{"title":"Biocompatible two-dimensional platelets with tunable sizes from polycarbonate-based block copolymers","authors":"Chuanqi Zhao, Hannah Schnicke, J. Diego Garcia-Hernandez, Jiandong Cai, Yifan Zhang, Charlotte E. Boott, Ian Manners","doi":"10.1039/d5py00078e","DOIUrl":"https://doi.org/10.1039/d5py00078e","url":null,"abstract":"Two-dimensional (2D) nanoparticles have received considerable attention due to their versatile applications ranging from catalysis, optoelectronics to nanomedicine. However, it remains challenging to access size tunable flat nanostructures with spatially tailored chemistries. The seeded-growth method, “living” crystallization-driven self-assembly (CDSA) has emerged as a promising approach for preparing well-defined 1D and 2D core–shell micellar assemblies from crystallizable block copolymers (BCPs). Nevertheless, the development of biocompatible aliphatic polycarbonates, such as poly(trimethylene carbonate) (PTMC), as core-forming blocks for CDSA is considerably less explored and represents a key challenge due to their low crystallinity. Herein, we report the development of poly(dimethyltrimethylene carbonate) (PDTC) as a crystallizable core-forming block through the introduction of side chains to PTMC. The BCPs containing crystallizable PDTC were shown to undergo living CDSA to prepare uniform and size-controlled 2D platelets. In addition, uniform segmented platelets with spatially localized coronal chemistries were successfully constructed. The colloidal stability of the platelets in aqueous solution allowed for an assessment of their toxicity toward healthy WI-38 and cancerous U-87 MG cells. These studies reveal that PDTC nanostructures exhibit no discernible cytotoxicity and excellent biocompatibility, indicating great potential for biomedical applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"51 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymer blends offer a cost-effective way to create new materials with enhanced properties. However, blending different polymers often results in phase separation with weak interfacial adhesion, leading to inferior mechanical properties. Given that high-density polyethylene (HDPE) and isotactic polypropylene (iPP) are the largest volume polymers, there is significant interest in developing blends of these materials. Applying a singlet nitrene-facilitated dynamic crosslinking method recently developed in our lab, in this study we prepared a series of HDPE/iPP blends across a range of compositions with enhanced compatibility and tunable thermomechanical properties. By incorporating a small amount of a dynamic crosslinker featuring a siloxane core and bis-aromatic sulfonyl azides (bis-ASA) into varying compositions of HDPE and iPP, we achieve significant improvements in the compatibility. AFM and SEM imaging analyses reveal that the compatibilized blends exhibit superior homogeneity compared to control blends. Additionally, these blends show significant improvements in elongation at break, toughness, and oxidative stability. The dynamic crosslinking further enhances the blends’ creep resistance while retains reprocessability, paving the way for the development of tailorable polymer blends for various applications.
{"title":"Tunable Polyethylene-polypropylene Blends via Compatibilization through Nitrene Insertion-Enabled Dynamic Covalent Crosslinking","authors":"Roman Shrestha, Zhibin Guan","doi":"10.1039/d4py01355g","DOIUrl":"https://doi.org/10.1039/d4py01355g","url":null,"abstract":"Polymer blends offer a cost-effective way to create new materials with enhanced properties. However, blending different polymers often results in phase separation with weak interfacial adhesion, leading to inferior mechanical properties. Given that high-density polyethylene (HDPE) and isotactic polypropylene (iPP) are the largest volume polymers, there is significant interest in developing blends of these materials. Applying a singlet nitrene-facilitated dynamic crosslinking method recently developed in our lab, in this study we prepared a series of HDPE/iPP blends across a range of compositions with enhanced compatibility and tunable thermomechanical properties. By incorporating a small amount of a dynamic crosslinker featuring a siloxane core and bis-aromatic sulfonyl azides (bis-ASA) into varying compositions of HDPE and iPP, we achieve significant improvements in the compatibility. AFM and SEM imaging analyses reveal that the compatibilized blends exhibit superior homogeneity compared to control blends. Additionally, these blends show significant improvements in elongation at break, toughness, and oxidative stability. The dynamic crosslinking further enhances the blends’ creep resistance while retains reprocessability, paving the way for the development of tailorable polymer blends for various applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chemocatalytic routes to poly(3-hydroxybutyrate) (P3HB), a natural biodegradable polyester that has long been considered as a sustainable alternative to non-(bio)degradable polyolefins, can deliver P3HB materials with catalyst-controlled diverse stereomicrostructures for tunable properties. P3HB topology brings in another way of modulating its properties, but selective synthesis of cyclic P3HB is challenging; yet harder is to simultaneously control both tacticity and topology. Here we introduce an effective strategy to selectively synthesize cyclic isotactic or syndio-rich P3HB by using bulky C2-symmetric salen-ligated metal catalysts bearing an initiating ligand that is also a good leaving group, and relatively long and ionic metal–polymer bond, both facilitating chain end-to-end cyclization. The resulting cyclic P3HB topology has been comprehensively characterized and differentiated from its linear counterpart, including direct visualization. When compared to its linear counterpart, cyclic P3HB of both stereomicrostructures shows superior properties, including higher melting and decomposition temperatures, better processability, and higher overall mechanical toughness.
{"title":"Stereoregular Cyclic Poly(3-hydroxybutyrate) Enabled by Catalyst-Controlled Tacticity and Topology","authors":"Celine Parker, Zhen Zhang, Ethan C Quinn, Liam Reilly, Eugene Y.-X. Chen","doi":"10.1039/d4py01304b","DOIUrl":"https://doi.org/10.1039/d4py01304b","url":null,"abstract":"Chemocatalytic routes to poly(3-hydroxybutyrate) (P3HB), a natural biodegradable polyester that has long been considered as a sustainable alternative to non-(bio)degradable polyolefins, can deliver P3HB materials with catalyst-controlled diverse stereomicrostructures for tunable properties. P3HB topology brings in another way of modulating its properties, but selective synthesis of cyclic P3HB is challenging; yet harder is to simultaneously control both tacticity and topology. Here we introduce an effective strategy to selectively synthesize cyclic isotactic or syndio-rich P3HB by using bulky C2-symmetric salen-ligated metal catalysts bearing an initiating ligand that is also a good leaving group, and relatively long and ionic metal–polymer bond, both facilitating chain end-to-end cyclization. The resulting cyclic P3HB topology has been comprehensively characterized and differentiated from its linear counterpart, including direct visualization. When compared to its linear counterpart, cyclic P3HB of both stereomicrostructures shows superior properties, including higher melting and decomposition temperatures, better processability, and higher overall mechanical toughness.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jungwook Lee, Yonghwan Kwon, Changhoon Yu, Dominik Konkolewicz, Min Sang Kwon
This study investigates the formation and evolution of dead chains during and after the photoiniferter-RAFT polymerization of poly(methyl acrylate). Thermal gradient high-performance liquid chromatography (TG-HPLC) was employed to quantify living and dead chains within the system. Through HPLC fractionation, dead chains were directly separated and further analyzed using 1H NMR spectroscopy and gel permeation chromatography. The results demonstrated a linear increase in dead chain formation over time, likely attributed to the continuous removal of thiocarbonylthio (TCT) end groups from living chains. The relationship between light intensity and dead chain formation was also investigated; however, the dead fraction exhibited a linear increase regardless of light intensity. These findings underscore the critical importance of managing these dynamics to preserve the “living” nature of photoiniferter-RAFT systems.
{"title":"The livingness of poly(methyl acrylate) under visible light photoiniferter-RAFT polymerization mediated by trithiocarbonates","authors":"Jungwook Lee, Yonghwan Kwon, Changhoon Yu, Dominik Konkolewicz, Min Sang Kwon","doi":"10.1039/d5py00151j","DOIUrl":"https://doi.org/10.1039/d5py00151j","url":null,"abstract":"This study investigates the formation and evolution of dead chains during and after the photoiniferter-RAFT polymerization of poly(methyl acrylate). Thermal gradient high-performance liquid chromatography (TG-HPLC) was employed to quantify living and dead chains within the system. Through HPLC fractionation, dead chains were directly separated and further analyzed using <small><sup>1</sup></small>H NMR spectroscopy and gel permeation chromatography. The results demonstrated a linear increase in dead chain formation over time, likely attributed to the continuous removal of thiocarbonylthio (TCT) end groups from living chains. The relationship between light intensity and dead chain formation was also investigated; however, the dead fraction exhibited a linear increase regardless of light intensity. These findings underscore the critical importance of managing these dynamics to preserve the “living” nature of photoiniferter-RAFT systems.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shweta Gaikwad, Argha Bhattacharjee, Stanley Baldwin, Steven Huss, Anna Griggs, Michael Spicuzza, Elizabeth Elacqua
Iridium-based polypyridyl complexes have gained recent attention in photoredox catalysis, with the potential for enhanced efficiency across a variety of applications. However, challenges such as poor recyclability, catalyst loss, and high costs can hinder their practical utility. Herein, we report the synthesis and characterization of three poly(methyl methacrylate)s featuring pendant cyclometalated iridium complexes based upon [Ir(df(CF3)ppy)2(dmbpy)](PF6), [Ir(ppy)2(dmbpy)](PF6), and fac-Ir(ppy)3. Our homogeneous polymer catalysts exhibited exceptional performance across a diverse array of photoredox-mediated transformations, including Birch-type photo-reduction, cycloaddition reactions, dual catalytic cross-coupling systems, and regioselective alkene functionalizations, while closely mimicking the catalytic and photophysical properties of their small-molecule counterparts with easy product isolation. The new polymer photocatalyst maintained fidelity during reactions, enabling it to be recycled and reused up to at least five cycles. This approach combines high performance with sustainability, offering a promising pathway toward greener photoredox catalysts while broadening the practical applications of iridium-based systems.
{"title":"Recyclable Iridium-Containing Copolymers for Homogeneous Photoredox Catalysis","authors":"Shweta Gaikwad, Argha Bhattacharjee, Stanley Baldwin, Steven Huss, Anna Griggs, Michael Spicuzza, Elizabeth Elacqua","doi":"10.1039/d4py01391c","DOIUrl":"https://doi.org/10.1039/d4py01391c","url":null,"abstract":"Iridium-based polypyridyl complexes have gained recent attention in photoredox catalysis, with the potential for enhanced efficiency across a variety of applications. However, challenges such as poor recyclability, catalyst loss, and high costs can hinder their practical utility. Herein, we report the synthesis and characterization of three poly(methyl methacrylate)s featuring pendant cyclometalated iridium complexes based upon [Ir(df(CF<small><sub>3</sub></small>)ppy)<small><sub>2</sub></small>(dmbpy)](PF<small><sub>6</sub></small>), [Ir(ppy)<small><sub>2</sub></small>(dmbpy)](PF<small><sub>6</sub></small>), and fac-Ir(ppy)<small><sub>3</sub></small>. Our homogeneous polymer catalysts exhibited exceptional performance across a diverse array of photoredox-mediated transformations, including Birch-type photo-reduction, cycloaddition reactions, dual catalytic cross-coupling systems, and regioselective alkene functionalizations, while closely mimicking the catalytic and photophysical properties of their small-molecule counterparts with easy product isolation. The new polymer photocatalyst maintained fidelity during reactions, enabling it to be recycled and reused up to at least five cycles. This approach combines high performance with sustainability, offering a promising pathway toward greener photoredox catalysts while broadening the practical applications of iridium-based systems.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Martina Huber, Patricia Sonnenberg, Stefan Naumann
Ordered mesoporous carbons (OMCs), typically prepared as fine powders, provide a striking combination of beneficial properties which can be considered as crucial for many current and future technological applications. These properties, which include light weight, high surface areas, tunable pore sizes and pore arrangements, variable surface chemistry and electric conductivity, can be further boosted if more complex OMC morphologies are realized. Perhaps most rewarding in this regard are film-like structures, either as defined layers on specific surfaces or even as self-supporting, free-standing films/membranes. Such materials are of high relevance, yet their synthesis and characterization is also significantly more demanding than powder formation. As a consequence, this research field is only just emerging and the number of publications describing self-supporting and well-defined OMC film structures is still rather limited. The presented mini-review thus aims to highlight this exciting type of material in a compact manner, focusing on aspects of synthesis, characterization and application, with the overall aim of encouraging further research efforts. Such efforts are particularly dependent on the polymer community, as the realization of well-defined OMC properties very much depends on polymers (e.g., as templates) and polymerization processes (e.g., cross-linking of carbon precursors). The translation of well-defined template block copolymers into well-defined OMC properties (especially pore size and pore geometry/connectivity) is an ongoing research focus, which is highly important for film morphologies.
{"title":"Polymer-Templated Films of Ordered Mesoporous Carbon: Preparation, Characterization and Applications","authors":"Martina Huber, Patricia Sonnenberg, Stefan Naumann","doi":"10.1039/d5py00107b","DOIUrl":"https://doi.org/10.1039/d5py00107b","url":null,"abstract":"Ordered mesoporous carbons (OMCs), typically prepared as fine powders, provide a striking combination of beneficial properties which can be considered as crucial for many current and future technological applications. These properties, which include light weight, high surface areas, tunable pore sizes and pore arrangements, variable surface chemistry and electric conductivity, can be further boosted if more complex OMC morphologies are realized. Perhaps most rewarding in this regard are film-like structures, either as defined layers on specific surfaces or even as self-supporting, free-standing films/membranes. Such materials are of high relevance, yet their synthesis and characterization is also significantly more demanding than powder formation. As a consequence, this research field is only just emerging and the number of publications describing self-supporting and well-defined OMC film structures is still rather limited. The presented mini-review thus aims to highlight this exciting type of material in a compact manner, focusing on aspects of synthesis, characterization and application, with the overall aim of encouraging further research efforts. Such efforts are particularly dependent on the polymer community, as the realization of well-defined OMC properties very much depends on polymers (e.g., as templates) and polymerization processes (e.g., cross-linking of carbon precursors). The translation of well-defined template block copolymers into well-defined OMC properties (especially pore size and pore geometry/connectivity) is an ongoing research focus, which is highly important for film morphologies.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143590236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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