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Conjugated polymers with glycol-based chains, are emerging as a material class with promising applications as organic mixed ionic-electronic conductors, particularly in bioelectronics and thermoelectrics. However, little is still known about their microstructure and the role of the side chains in determining intermolecular interactions and polymer packing. Here, we use the combination of electrospray deposition and scanning tunneling microscopy to determine the microstructure of prototypical glycolated conjugated polymers (pgBTTT and p(g2T-TT)) with submonomer resolution. Molecular dynamics simulations of the same surface-adsorbed polymers exhibit an excellent agreement with the experimental images, allowing us to extend the characterization of the polymers to the atomic scale. Our results prove that, similarly to their alkylated counterparts, glycolated polymers assemble through interdigitation of their side chains, although significant differences are found in their conformation and interaction patterns. A model is proposed that identifies the driving force for the polymer assembly in the tendency of the side chains to adopt the conformation of their free analogues, i.e., polyethylene and polyethylene glycol, for alkyl or ethylene glycol side chains, respectively. For both classes of polymers, it is also demonstrated that the backbone conformation is determined to a higher degree by the interaction between the side chains rather than by the backbone torsional potential energy. The generalization of these findings from two-dimensional (2D) monolayers to three-dimensional thin films is discussed, together with the opportunity to use this type of 2D study to gain so far inaccessible, subnm-scale information on the microstructure of conjugated polymers.

Exchanging hydrophobic alkyl-based side chains to hydrophilic glycol-based side chains is a widely adopted method for improving mixed-transport device performance, despite the impact on solid state packing and polymer-electrolyte interactions being poorly understood. Presented here is a Molecular Dynamics (MD) force field for modelling alkoxylated and glycolated polythiophenes. The force field is validated against known packing motifs for their monomer crystals. MD simulations, coupled with X-ray Diffraction (XRD), show that alkoxylated polythiophenes will pack with a `tilted stack' and straight interdigitating side chains, whilst their glycolated counterpart will pack with a `deflected stack' and an s-bend side chain configuration. MD simulations reveal water penetration pathways into the alkoxylated and glycolated crystals - through the {\pi}-stack and through the lamellar stack respectively. Finally, the two distinct ways tri-ethylene glycol polymers can bind to cations are revealed, showing the formation of a meta-stable single bound state, or an energetically deep double bound state, both with a strong side chain length dependance. The minimum energy pathways for the formation of the chelates are identified, showing the physical process through which cations can bind to one or two side chains of a glycolated polythiophene, with consequences for ion transport in bithiophene semiconductors., Comment: 10 pages, 4 figures

Semiconducting polymers with oligoethylene glycol sidechains have attracted strong research interest for organic electrochemical transistor (OECT) applications. However, key molecular design rules for high-performance OECTs via efficient mixed electronic/ionic charge transport are still unclear. Herein, we synthesize and characterize new glycolated copolymers (gDPP-TTT and gDPP-TTVTT) with diketopyrrolopyrrole (DPP) acceptor and thiophene-based (TTT or TTVTT) donor units for accumulation mode OECTs, where a long-alkyl-group (C12 ) attached to DPP unit acts as a spacer distancing the oligoethylene glycol from the polymer backbone. gDPP-TTVTT shows the highest OECT transconductance (61.9 S cm-1 ) and high operational stability, compared to gDPP-TTT and their alkylated counterparts. Surprisingly, gDPP-TTVTT also shows high electronic charge mobility in field-effect transistor, suggesting efficient ion injection/diffusion without hindering its efficient electronic charge transport. The elongated donor unit (TTVTT) facilitates the hole polaron formation more localized to the donor unit, leading to faster and easier polaron formation with less impact on polymer structure during OECT operation, as opposed to the TTT unit. This is supported by molecular dynamics (MD) simulation. We conclude that these simultaneously high electronic and ionic charge transport properties are achieved due to the long-alkyl-group spacer in amphipathic sidechains, providing an important molecular design rule for glycolated copolymers. This article is protected by copyright. All rights reserved.