U.S. Department of Energy Office of Scientific and Technical Information
Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors
In this study, we introduce two thiophene-phenylene-thiophene (TPT) polymers designed to leverage noncovalent intramolecular interactions to regulate main-chain conformation and enhance solid-state ordering. By incorporating unsubstituted thiophene (T) or bithiophene (2T) units, we reveal striking divergence in the thermal, morphological, and optoelectronic properties of the resulting films, facilitated by these noncovalent interactions. Using a combination of computational and experimental approaches, we show that annealing yields remarkably different polymer conformations and, consequently, charge transport properties. TPT-T undergoes a significant structural transformation, adopting a more planar backbone conformation and a highly crystalline, edge-on molecular orientation. In contrast, the introduction of a single additional thiophene unit in TPT-2T leads to a more isotropic molecular orientation with a slight preference for face-on alignment, resulting in a heterogeneous film structure that hinders charge transport despite achieving tighter molecular packing. Remarkably, despite being composed of achiral components, TPT-2T develops chirality upon annealing, indicating the formation of a helical conformation. Organic field-effect transistor measurements reveal that the well-ordered alignment in annealed TPT-T films results in higher charge carrier mobility and a narrower distribution of mobility values than in TPT-2T. These findings provide critical insights into the structure−property relationships of conjugated polymers, offering guidance for optimizing molecular design and processing strategies for highperformance organic electronic materials.
Makala, Manikanta, et al. "Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors." Chemistry of Materials, vol. 37, no. 11, May. 2025. https://doi.org/10.1021/acs.chemmater.5c00631
Makala, Manikanta, Xu, Zhuang, Saiev, Shamil, Ni, Xiaojuan, Sabury, Sina, Coropceanu, Veaceslav, Brédas, Jean-Luc, Diao, Ying, Reynolds, John R., Jurchescu, Oana D., & Österholm, Anna M. (2025). Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors. Chemistry of Materials, 37(11). https://doi.org/10.1021/acs.chemmater.5c00631
Makala, Manikanta, Xu, Zhuang, Saiev, Shamil, et al., "Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors," Chemistry of Materials 37, no. 11 (2025), https://doi.org/10.1021/acs.chemmater.5c00631
@article{osti_2569540,
author = {Makala, Manikanta and Xu, Zhuang and Saiev, Shamil and Ni, Xiaojuan and Sabury, Sina and Coropceanu, Veaceslav and Brédas, Jean-Luc and Diao, Ying and Reynolds, John R. and Jurchescu, Oana D. and others},
title = {Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors},
annote = {In this study, we introduce two thiophene-phenylene-thiophene (TPT) polymers designed to leverage noncovalent intramolecular interactions to regulate main-chain conformation and enhance solid-state ordering. By incorporating unsubstituted thiophene (T) or bithiophene (2T) units, we reveal striking divergence in the thermal, morphological, and optoelectronic properties of the resulting films, facilitated by these noncovalent interactions. Using a combination of computational and experimental approaches, we show that annealing yields remarkably different polymer conformations and, consequently, charge transport properties. TPT-T undergoes a significant structural transformation, adopting a more planar backbone conformation and a highly crystalline, edge-on molecular orientation. In contrast, the introduction of a single additional thiophene unit in TPT-2T leads to a more isotropic molecular orientation with a slight preference for face-on alignment, resulting in a heterogeneous film structure that hinders charge transport despite achieving tighter molecular packing. Remarkably, despite being composed of achiral components, TPT-2T develops chirality upon annealing, indicating the formation of a helical conformation. Organic field-effect transistor measurements reveal that the well-ordered alignment in annealed TPT-T films results in higher charge carrier mobility and a narrower distribution of mobility values than in TPT-2T. These findings provide critical insights into the structure−property relationships of conjugated polymers, offering guidance for optimizing molecular design and processing strategies for highperformance organic electronic materials.},
doi = {10.1021/acs.chemmater.5c00631},
url = {https://www.osti.gov/biblio/2569540},
journal = {Chemistry of Materials},
issn = {ISSN 0897-4756},
number = {11},
volume = {37},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2025},
month = {05}}