Direct ladderization of cyclooctatetraene-containing, processable conjugated ladder polymers from annulated bis-zirconacyclopentadienes

Rothenberger, August J.; Bergman, Harrison M.; Li, He; Qi, Miao; Wang, Yunfei; Liu, Yi; Tilley, T. Don

doi:10.1039/d4sc06902a

Direct ladderization of cyclooctatetraene-containing, processable conjugated ladder polymers from annulated bis-zirconacyclopentadienes

Journal Article · Tue Nov 12 00:00:00 EST 2024 · Chemical Science

DOI:https://doi.org/10.1039/d4sc06902a· OSTI ID:2478562

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Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Conjugated ladder polymers (CLPs) are difficult yet captivating synthetic targets due to their fully unsaturated fused backbones. Inherent challenges associated with their synthesis often lead to low yields, structural defects, and insoluble products. Here a new method to form CLPs is demonstrated, utilizing a high-yielding dimerization of annulated zirconacyclopentadienes to form cyclooctatetraene (COT) monomer units. The resulting COT-containing polymers form rapidly in a single ladderization step from the bis-zirconacyclopentadiene precursors and display M_n up to 29.7 kg mol^-1. The polymers represent rare examples of CLPs with negatively curved rings, resulting in the observation of unusual properties. The rigid tub-shaped COT units embedded in the backbone imbue the polymers with microporosity, exhibiting BET surface areas up to 555 m² g^-1. Additionally, the remarkable solubility of these CLPs in organic solvents enables the fabrication of thin films showcasing high dielectric performance with a discharged energy density as high as 6.54 J cm^-3 at 650 MV m^-1.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2478562

Alternate ID(s):: OSTI ID: 2480485

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 48 Vol. 15; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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