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From carbonyl to sulfonyl: Unlocking advanced polymers with SuFEx-enabled macroisosteres
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DOI：10.1016/j.progpolymsci.2026.102078.png)
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Abstract
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To help guide future synthetic efforts toward advanced polymers with enhanced performance across uncharted chemical space, this review introduces the concept of macroisostere design, in which functional groups in high-commodity polymers are replaced with structurally analogous motifs. As a case study, we focus on the nascent family of sulfonyl (-SO2-)-containing polymers as macroisosteres of traditional carbonyl (-CO-)-based macromolecules. Historically, this class of polymers has remained largely under-explored due to limited synthetic accessibility compared to their carbonyl counterparts. The advent of Sulfur(VI) Fluoride Exchange (SuFEx) click chemistry has changed this landscape, enabling the efficient synthesis and systematic study of sulfonyl polymers and their physicochemical properties. In this review, we contrast classical synthetic routes with SuFEx-based strategies, showcasing how this powerful click chemistry provides access to materials with tunable properties including thermal, mechanical, and optoelectronic behaviors alongside sustainability. We also highlight the unique opportunities SuFEx offers for precision polymer synthesis, including the construction of macromolecules with chiral backbones arising from stereogenic S(VI) centers and the development of sequence-controlled architectures and post-polymerization modifications enabled by the orthogonality of SuFEx relative to other click reactions. (c) 2026 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Keywords:
SuFEx
Macroisostere
Click chemistry
Precision polymer
Sequence-controlled polymerization
Post-polymerization modification
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