ipso ‐Arylative Ring‐Opening Polymerization as a Route to Electron‐Deficient Conjugated Polymers

Shih, Feng‐Yang; Choi, Deokkyu; Wu, Qin; Nam, Chang‐Yong; Grubbs, Robert B.

doi:10.1002/ange.201809610

Title: ipso ‐Arylative Ring‐Opening Polymerization as a Route to Electron‐Deficient Conjugated Polymers

Journal Article · Tue Dec 04 00:00:00 EST 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201809610· OSTI ID:1484392

Shih, Feng‐Yang ^[1];

^[1];

^[2];

^[1]

Chemistry department Stony Brook University Stony Brook NY 11794 USA
Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY 11973 USA

Abstract ipso ‐Arylative ring‐opening polymerization of 2‐bromo‐8‐aryl‐8 H ‐indeno[2,1‐b]thiophen‐8‐ol monomers proceeds to M _n up to 9 kg mol ⁻¹ with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2‐benzoylphenyl or 2‐(4‐hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=−5.9/−4.0 eV) than poly(3‐hexylthiophene) owing to the electron‐withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10 ⁻³ cm ² V ⁻¹ s ⁻¹ ) for poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10 ⁻⁶ cm ² V ⁻¹ s ⁻¹ ), which suggests such polymers are candidates for n‐type organic semiconductors. Density functional theory calculations suggest that backbone distortion resulting from side‐chain steric interactions could be a key factor influencing charge mobilities.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0012704

OSTI ID:: 1484392

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 131 Journal Issue: 1; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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