Photocatalyst-independent photoredox ring-opening polymerization of O-carboxyanhydrides: stereocontrol and mechanism

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dc.contributor.authorZhong, Yongliangen
dc.contributor.authorFeng, Quanyouen
dc.contributor.authorWang, Xiaoqianen
dc.contributor.authorYang, Leien
dc.contributor.authorKorovich, Andrew G.en
dc.contributor.authorMadsen, Louis A.en
dc.contributor.authorTong, Rongen
dc.contributor.departmentChemical Engineeringen
dc.contributor.departmentChemistryen
dc.date.accessioned2021-04-22T12:22:46Zen
dc.date.available2021-04-22T12:22:46Zen
dc.date.issued2021-03-14en
dc.description.abstractPhotoredox ring-opening polymerization of O-carboxyanhydrides allows for the synthesis of polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. While powerful, obviating the use of precious metal-based photocatalysts would be attractive from the perspective of simplifying the protocol. Herein, we report the Co and Zn catalysts that are activated by external light to mediate efficient ring-opening polymerization of O-carboxyanhydrides, without the use of exogenous precious metal-based photocatalysts. Our methods allow for the synthesis of isotactic polyesters with high molecular weights (>200 kDa) and narrow molecular weight distributions (M-w/M-n < 1.1). Mechanistic studies indicate that light activates the oxidative status of a Co-III intermediate that is generated from the regioselective ring-opening of the O-carboxyanhydride. We also demonstrate that the use of Zn or Hf complexes together with Co can allow for stereoselective photoredox ring-opening polymerizations of multiple racemic O-carboxyanhydrides to synthesize syndiotactic and stereoblock copolymers, which vary widely in their glass transition temperatures.en
dc.description.notesThis work was supported by start-up funding from Virginia Tech, ACS-Petroleum Research Foundation (57926-DNI-7), and the National Science Foundation (CHE-1807911). We thank Dr N. Murthy Shanaiah for NMR experiments, Mehdi AshrafKhorassani for electrospray ionization mass spectrometry studies, Dr Jeffrey Parks for inductively coupled plasma mass spectrometry measurements, Dr Amanda Morris for.uorescence spectra measurements, Dr Guoliang Liu for differential scanning calorimetry, and Dr Webster Santos and Dr John Matson (all from Virginia Tech, Department of Chemistry) for providing anhydrous solvents.en
dc.description.sponsorshipACS-Petroleum Research FoundationAmerican Chemical Society [57926-DNI-7]; National Science FoundationNational Science Foundation (NSF) [CHE-1807911]; Virginia Techen
dc.format.mimetypeapplication/pdfen
dc.identifier.doihttps://doi.org/10.1039/d0sc05550fen
dc.identifier.eissn2041-6539en
dc.identifier.issn2041-6520en
dc.identifier.issue10en
dc.identifier.urihttp://hdl.handle.net/10919/103079en
dc.identifier.volume12en
dc.language.isoenen
dc.rightsCreative Commons Attribution-NonCommercial 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by-nc/4.0/en
dc.titlePhotocatalyst-independent photoredox ring-opening polymerization of O-carboxyanhydrides: stereocontrol and mechanismen
dc.title.serialChemical Scienceen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten
dc.type.dcmitypeStillImageen

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