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http://dx.doi.org/10.1002/chem.201203975 | DOI Listing |
Nat Chem
May 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
Degradation of carbon-backbone polymers, which make up most plastics, remains a formidable challenge owing to strong and inert main-chain C-C bonds. While incorporation of comonomers that generate backbone radicals under certain conditions can induce degradation of the polymer chain, such strategies yield complex oligomer mixtures. Here we report aromatization-driven C-C bond cleavage as a viable and powerful strategy to endow the degradability into carbon backbones using acrylic polymers as a model example.
View Article and Find Full Text PDFDes Monomers Polym
July 2023
Department of Chemical Science and Engineering, Graduate School of Materials and Chemical Technology, Tokyo Institute of Technology, Yokohama, JAPAN.
The donor-acceptor type π-conjugated polymers having heterole units were prepared by the reaction of a regioregular organometallic polymer having both reactive titanacyclopentadiene and electron-donor thiophene-2,5-diyl units in the main chain with electrophiles such as diphenyltin dichloride, dichlorophenylphosphine, and diiodophenylarsine. For example, a polymer having electron-accepting phosphole unit was obtained in 54% yield whose number-average molecular weight () and molecular weight distribution (/) were estimated as 3,000 and 1.9, respectively.
View Article and Find Full Text PDFChem Commun (Camb)
April 2022
Department of Chemistry, The University of North Carolina at Charlotte, Charlotte, NC 28223, USA.
Here, we show for the first time that main-chain organometallic polymers (MCOPs) can be prepared from Janus N-heterocyclic carbene (NHC) linkers and polynuclear cluster nodes. The crosslinked framework CoS-MCOP is synthesized ligand displacement reactions and undergoes reversible electron transfer in the solid state. Discrete molecular cluster species can be excised from the framework by digesting the solid in solutions of excess monocarbene.
View Article and Find Full Text PDFChem Commun (Camb)
March 2022
Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
The Pd-catalyzed carbene coupling reaction of -tosylhydrazones and benzyl bromides has been developed into a polymerization process for the first time, providing an efficient method for the synthesis of poly(arylene vinylene)s (PAVs). This method affords PAVs bearing -vinylene units predominantly. It can also introduce a CF group on each vinylene carbon atom in the polymer main chain.
View Article and Find Full Text PDFJ Am Chem Soc
August 2021
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States.
Recent research on the mechanochemistry of metallocene mechanophores has shed light on the force-responsiveness of these thermally and chemically stable organometallic compounds. In this work, we report a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltocenium-containing polymers. Ester derivatives of the cationic cobaltocenium, though isoelectronic to neutral ferrocene, are unstable in the nonmechanical control experimental conditions that were accommodated by their ferrocene analogs.
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