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Authors
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Zhang, K.; Komber, H.; Voit, B.; Kiriy, A.
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Title
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Externally initiated, Pd-catalyzed chain-growth polycondensation using Buchwald precatalysts: Preparation of acetylene-end-group-functionalized poly(bithiophene-naphthalenediimide)
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Date
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02.04.2026
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Number
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0
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Abstract
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We report an externally initiated, Pd-catalyzed chain-growth polycondensation using Buchwald-type precatalysts for the synthesis of acetylene-end-functionalized poly(bithiophene-naphthalene diimide), P(TNDIT), conjugated polymers. Screening of six commercial precatalysts identified (t-BuXPhos)Pd (precatalyst 1), having in the structure phosphine ligands bearing two tert-butyl and one biphenyl ligand, as enabling efficient polymerization under mild conditions with moderate molecular weight control. The method supports the transfer of synthetically versatile, complex end-groups directly in the initiating step, an approach rarely achieved in catalyst-transfer polycondensation and unprecedented for donor–acceptor monomers such as TNDIT. NMR and MALDI-TOF end-group analysis, aided by fractionation, confirm that functionalization occurs during initiation and supports a chain-growth mechanism facilitated by Pd ring-walking. By varying initiator loading and timing, either mono- or bis-functionalized polymers can be selectively accessed. This strategy enables the high-yield synthesis of functionalized n-type conjugated polymers with tailored end-groups, offering new opportunities for postpolymer modification, block copolymer construction, cross-linking, and supramolecular assembly.
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Publisher
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American Chemical Society
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Wikidata
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Citation
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Macromolecules 59 (2026) 4071-4083
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DOI
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https://doi.org/10.1021/acs.macromol.5c03552
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