Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p­(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3′ positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p­(g2T-TT) from the 3,3′ to the 4,4′ positions and compared with the original p­(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S–O interactions were redistributed along the backbone, and the influence on the polymer’s microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (μ) of 3.44 ± 0.13 cm2 V–1 s–1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p­(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.

The development, optimization, and assessment of new methods for the preparation of conjugated materials is key to the continued progress of organic electronics. Direct C–H activation methods have emerged and developed over the last 10 years to become an invaluable synthetic tool for the preparation of conjugated polymers for both redox-active and solid-state applications. Here, we evaluate direct (hetero)­arylation polymerization (DHAP) methods for the synthesis of indaceno­[1,2-b:5,6-b′]­dithiophene-based polymers. We demonstrate, using a range of techniques, including direct visualization of individual polymer chains via high-resolution scanning tunneling microscopy, that DHAP can produce polymers with a high degree of regularity and purity that subsequently perform in organic thin-film transistors comparably to those made by other cross-coupling polymerizations that require increased synthetic complexity. Ultimately, this work results in an improved atom economy by reducing the number of synthetic steps to access high-performance molecular and polymeric materials.

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.

The strong molecule-surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin molecules to the copper substrate.