Interplay between synthetic conditions and micromorphology in poly(3,4-ethylenedioxythiophene):tosylate (PEDOT:Tos): an atomistic investigation

文献情報

出版日 2019-03-26

DOI 10.1039/C9CP00970A

インパクトファクター 3.676

著者

A. Cappai, A. Antidormi, A. Bosin, D. Galliani, D. Narducci, C. Melis

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要旨

Micromorphology of conjugated polymers is expected to play a crucial role in both heat and charge transport properties. In this perspective, the details of the polymerization mechanism acquire a fundamental relevance, providing the link between the basic chemical reaction paths and the resulting molecular structure and arrangement. For PEDOT, the role played by the Brønsted bases (proton scavengers) and their impact on the distribution of polymer chain lengths are still a matter of debate. In the present work, we have systematically analyzed several reaction paths leading to PEDOT polymerization. By means of atomistic simulations, we identified the thermodynamically preferred reaction path, proving that tosylate anions rule proton scavenging. PEDOT chain length was computed to be ∼12–13 monomeric units. We could also demonstrate how the proton scavengers set at once the chain lengths and the sample crystallinity. Furthermore, we found that tosylate gives rise to a sharper multimodal distribution of chain length, a feature that supports hypotheses regarding the occurrence of a percolative transport regime mediated by tie chains bridging paracrystalline regions.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.