Issue 14, 2024

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Abstract

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm−1. More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10−2 cm2 V−1 s−1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Graphical abstract: Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Supplementary files

Article information

Article type
Communication
Submitted
21 Nov 2023
Accepted
18 Apr 2024
First published
30 Apr 2024
This article is Open Access
Creative Commons BY license

Mater. Horiz., 2024,11, 3352-3363

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

S. Sabury, Z. Xu, S. Saiev, D. Davies, A. M. Österholm, J. M. Rinehart, M. Mirhosseini, B. Tong, S. Kim, J. Correa-Baena, V. Coropceanu, O. D. Jurchescu, J. Brédas, Y. Diao and J. R. Reynolds, Mater. Horiz., 2024, 11, 3352 DOI: 10.1039/D3MH01974H

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