the operation of a range of bioelectronic devices, [1][2][3] such as organic electrochemical transistors (OECTs), [4][5][6] batteries, [7] and supercapacitors. [6] They have inherent advantages over traditional organic semiconductors for these electrochemical applications, [4,[8][9][10] in particular their ability to operate with an aqueous electrolyte. [11,12] Exchanging a traditional alkyl-based side chain for a glycol-based hydrophilic side chain has been widely adopted as a strategy for increasing uptake of water and ions in OMIECs, and subsequently increasing their capacitance. [5,7,[13][14][15] Whilst polythiophenes bearing long alkyl side chains are often reported to pack with interdigitating side chains [16][17][18][19][20][21][22] and π-stacks that are either straight or lightly tilted [17,20,[22][23][24] (see Figure S1, Supporting Information for backbone packing motifs referred to in this study), little is known about glycolated OMIEC packing, despite the chain packing being critical to both electronic and ionic transport. [21,[25][26][27][28] Experimental studies have suggested that glycolated OMIECs adopt smaller π-stack distances than their alkylated counterparts. [5,29] As well as solid-state packing, structural characterization of OMIECs should account for their swelling behavior, 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 modeling 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 π-stack and through the lamellar stack respectively. Finally, the two distinct ways triethylene glycol polymers can bind to cations are revealed, showing the formation of a metastable single bound state, or an energetically deep double bound state, both with a strong side-chain length dependence. 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.

Semiconducting polymers with oligoethylene glycol (OEG) 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. In this work, new glycolated copolymers (gDPP-TTT and gDPP-TTVTT) with diketopyrrolopyrrole (DPP) acceptor and thiophene (T) and vinylene (V) thiophene-based donor units are synthesized and characterized for accumulation mode OECTs, where a long-alkyl-group (C 12 ) attached to the DPP unit acts as a spacer distancing the OEG groups 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 a field-effect transistor, suggesting efficient ion injection/diffusion without hindering its efficient electronic charge transport. The elongated donor unit (TTVTT) facilitates hole polaron formation to be 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 simulation. 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.

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.

Conjugated polymers (CPs) that show stable and reversible cation insertion/deinsertion under ambient conditions hold great potential for optoelectronic and energy storage devices. However, n-doped CPs are prone to parasitic reactions upon exposure to moisture or oxygen. This study reports a new family of napthalenediimide (NDI) based conjugated polymers capable of undergoing electrochemical n-type doping in ambient air. By functionalizing the NDI-NDI repeating unit with alternating triethylene glycol and octadecyl side chains, the polymer backbone shows stable electrochemical doping at ambient conditions. We systematically investigate the extent of volumetric doping involving monovalent cations of varying size (Li + , Na + , tetraethylammonium (TEA + )) with electrochemical methods, including cyclic voltammetry, differential pulse voltammetry, spectroelectrochemistry, and electrochemical impedance spectroscopy. We observed that introducing hydrophilic side chains on the polymer backbone improves the local dielectric environment of the backbones and lowers the energetic barrier for ion insertion. Surprisingly, when using Na + electrolyte, the polymer films exhibit higher volumetric doping efficiency, faster-switching kinetics, higher optical contrast, and selective multielectrochromism when compared to Li + or TEA + electrolytes. Using well-tempered metadynamics, we characterize the free energetics of side chain−ion interactions to find that Li + binds more tightly to the glycolated NDI moieties than Na + , hindering Li + ion transport, switching kinetics, and limiting the films' doping efficiency.

is paper reviews both experimental and theoretical work on nanostructures showing high quantum yields due to the phenomenon of multiple exciton generation. It outlines the aims and barriers to progress in identifying further such nanostructures and also includes important developments concerning solar devices where nanostructures act as the light-absorbing component. It reports on both semiconductor and carbon structures, both monocomposite (of various dimensionalities) and heterogeneous. Finally, it looks at future directions that can be taken to push solar cell efficiency above the classic limit set by Shockley and Queisser in 1961.