Fabrication of Supramolecular Semiconductor Block Copolymers by Ring‐Opening Metathesis Polymerization |
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Authors: | Dr Elizabeth Elacqua Prof?Dr Marcus Weck |
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Institution: | Molecular Design Institute and Department of Chemistry, New York University, 100?Washington Square East, New York, NY 10003 (USA) |
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Abstract: | ω‐Telechelic poly(p‐phenylene vinylene) species (PPVs) are prepared by living ring‐opening metathesis polymerization of a 2.2]paracyclophane‐1,9‐diene in the presence of Hoveyda–Grubbs 2nd generation initiator, with terminating agents based on N1,N3‐bis(6‐butyramidopyridin‐2‐yl)‐5‐hydroxyisophthalamide (Hamilton wedge), cyanuric acid, PdII–SCS‐pincer, or pyridine moieties installing the supramolecular motifs. The resultant telechelic polymers are self‐assembled into supramolecular block copolymers (BCPs) via metal coordination or hydrogen bonding and analyzed by 1H NMR spectroscopy. The optical properties are examined, whereby individual PPVs exhibit similar properties regardless of the nature of the end group. Upon self‐assembly, different behaviors emerge: the hydrogen‐bonding BCP behaves similarly to the parent PPVs whereas the metallosupramolecular BCP demonstrates a hypsochromic shift and a more intense emission owing to the suppression of aggregation. These results demonstrate that directional self‐assembly can be a facile method to construct BCPs with semiconducting networks, while combating solubility and aggregation. |
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Keywords: | block copolymers conjugated polymers ring‐opening metathesis self‐assembly supramolecular polymers |
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