Identifying the "true" repeat unit of a copolymer using time-resolved electron paramagnetic resonance spectroscopy: a case study involving PNDIT2, NDI-T2 and T-NDI-T

Semiconducting polymers promise to revolutionise the way electronic devices can be built and deployed for a vast array of applications ranging from light-energy conversion to sensors to thermoelectric generators. Conjugated push-pull copolymers consisting of alternating donor and acceptor moieties are at the heart of these applications, due to the large tunability of their electronic structure. Hence, knowing the repeat unit and thus the chromophore of these materials is essential for a detailed understanding of the structure--function relationship of conjugated polymers used in organic electronics applications. Therefore, spectroscopic tools providing the necessary molecular resolution that allows to discriminate between different building blocks and to decide which one actually resembles the electronic structure of the polymer are of utmost importance. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is both, perfectly suited for this task and clearly superior to optical spectroscopy, particularly when supported by quantum-chemical calculations. This is due to its molecular resolution and unique capability of using light-induced triplet states to probe the electronic structure as well as the impact of the local environment. Here, we demonstrate the power of this approach for the polymer PNDIT2 (poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)}) revealing NDI-T2 unambiguously as the "true" repeat unit of the polymer, representing the chromophore. The alternative building block T-NDI-T has a markedly different electronic structure. These results are of high importance for the rational design of conjugated polymers for organic electronics applications.

Modulation of the electrical double layer in metals and conducting polymers

The electrical double layer (EDL) formed at the interface between various materials and an electrolyte has been studied for a long time. In particular, the EDL formed at metal/electrolyte interfaces is central in electrochemistry, with a plethora of applications ranging from corrosion to batteries to sensors. The discovery of highly conductive conjugated polymers has opened a new area of electronics, involving solution-based or solution-interfaced devices, and in particular in bioelectronics, namely for use in deep-brain stimulation electrodes and devices to measure and condition cells activity, as these materials offer new opportunities to interface cells and living tissues. Here, it is shown that the potential associated to the double layer formed at the interface between either metals or conducting polymers and electrolytes is modified by the application of an electric field along the conductive substrate. The EDL acts as a transducer of the electric field applied to the conductive substrate. This observation has profound implications in the modelling and operation of devices relying on interfaces between conductive materials (metals and conjugated polymers) and electrolytes, which encompasses various application fields ranging from medicine to electronics.

Fabrication of Low-Fouling Surfaces on Alkyne-Functionalized Poly-(p-xylylenes) Using Click Chemistry

A facial, versatile, and universal method that breaks the substrate limits is desirable for antifouling treatment. Thin films of functional poly-p-xylylenes (PPX) that are deposited using chemical vapor deposition (CVD) provide a powerful platform for surface immobilization of molecules. In this study, we prepared an alkyne-functionalized PPX coating on which poly (sulfobetaine methacrylate-co-Az) could be conjugated via click chemistry. We found that the conjugated polymers were very stable and inhibited cell adhesion and protein adsorption effectively. The same conjugation strategy could also be applied to conjugate azide-containing poly (ethylene glycol) and poly (NIPAAm). The results indicate that our method provides a simple and robust tool for fabricating antifouling surfaces on a wide range of substrates using CVD technology of functionalized poly (p-xylylenes) for biosensor, diagnostics, immunoassay, and other biomaterial applications.

Precrystalline P3HT nanowires: growth-controllable solution processing and effective molecular packing transfer to thin-film

Solution-processable precrystalline nanowires (NWs) of conjugated polymers (CPs) have garnered significant attention in fundamental research based on crystallization-driven self-assembly and in the roll-to-roll fabrication of optoelectronic devices such as organic...