Synthesis and Conformation of Defect-Free, Strained, and Non-Aggregated Conjugated Ladder Polymers Article Swipe

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James Shao-Jiun Yang , Vijaya Sundar Jeyaraj , Guorong Ma , Daniel Doria , Xiaodan Gu , Daniel P. Tabor , Lei Fang ·

YOU? · · 2025 · Open Access · · DOI: https://doi.org/10.26434/chemrxiv-2025-3blt6

A fundamental understanding of the solution properties of conjugated ladder polymers (CLPs) is essential for advancing their design, synthesis, and solution processing toward high-performance optoelectronic applications. Nevertheless, elucidating the solution conformation of CLPs remains a significant challenge in the field of polymer physics, owing to the difficulty of synthesizing defect-free samples, their intrinsically low solubility that results in weak signals and limited analytical accuracy, the pronounced tendency of CLPs to aggregate even when dissolved, and the absence of reliable theoretical models. Here, these fundamental challenges are addressed by the synthesis, neutron scattering measurements, and computational simulations of two model CLPs, LP1 and LP2. Owing to their bulky three-dimensional side chains, LP1 and LP2 exhibit non-aggregated character and high dispersibility as single polymer chains. Small-angle neutron scattering revealed unexpectedly low persistence lengths (Lp) of 3–5 nm. The similar Lp to those of non-ladder conjugated polymers such as P3HT indicates the long-range conformational semi-flexibility of CLPs despite possessing ladder-type constitution. Machine learning-based molecular dynamics simulations further showed that the semi-flexibility of these CLP chains mainly results from the pronounced out-of-plane deformations, which is synergistically influenced by the steric congestion of the side chains. Overall, a comprehensive experimental and computational approach demonstrates that CLPs, despite their fused-ring polyaromatic backbones, are best described as ribbon-like, semi-flexible chains, in contrast to the common belief that they are rigid-rod polymers.

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Steric effects Conjugated system Polymer Chemical physics Side chain Flexibility (engineering) Materials science Crystallography Persistence length Scattering Chemistry Nanotechnology Stereochemistry Physics Optics Composite material Statistics Mathematics

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Type: preprint
Language: en
Landing Page: https://doi.org/10.26434/chemrxiv-2025-3blt6
PDF: https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/68ade335a94eede154b486b1/original/synthesis-and-conformation-of-defect-free-strained-and-non-aggregated-conjugated-ladder-polymers.pdf
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OpenAlex ID: https://openalex.org/W4413803139

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DOI: https://doi.org/10.26434/chemrxiv-2025-3blt6

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Title: Synthesis and Conformation of Defect-Free, Strained, and Non-Aggregated Conjugated Ladder Polymers

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Language: en

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Publication year: 2025

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Publication date: 2025-08-29

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Authors: James Shao-Jiun Yang, Vijaya Sundar Jeyaraj, Guorong Ma, Daniel Doria, Xiaodan Gu, Daniel P. Tabor, Lei Fang

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Landing page: https://doi.org/10.26434/chemrxiv-2025-3blt6

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PDF URL: https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/68ade335a94eede154b486b1/original/synthesis-and-conformation-of-defect-free-strained-and-non-aggregated-conjugated-ladder-polymers.pdf

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Concepts: Steric effects, Conjugated system, Polymer, Chemical physics, Side chain, Flexibility (engineering), Materials science, Crystallography, Persistence length, Scattering, Chemistry, Nanotechnology, Stereochemistry, Physics, Optics, Composite material, Statistics, Mathematics

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