Depending on its adsorption conformation on the Au(111) surface, a zwitterionic single-molecule machine works in two different ways under bias voltage pulses. It is a unidirectional rotor while anchored on the surface. It is a fast-drivable molecule vehicle (nanocar) while physisorbed. By tuning the surface coverage, the conformation of the molecule can be selected to be either rotor or nanocar. The inelastic tunneling excitation producing the movement is investigated in the same experimental conditions for both the unidirectional rotation of the rotor and the directed movement of the nanocar.

Organic electrochemical transistors (OECTs) require organic mixed ion-electron conductors (OMIECs) (i.e., hydrophilic materials supporting electron and ion transportation) as active materials. However, high-performance OMIECs grafted with hydrophilic side chains are difficult to synthesize and purify, and often suffer from swelling during operation. In contrast, the synthetic pathways toward a broad range of hydrophobic polymeric semiconductors used in classic organic-field-effect transistors are well established, and several are even commercially available. Yet, these hydrophobic materials do not intrinsically support ionic transport, limiting their application in OECTs. Here, poly(ethyleneglycol) (PEG)-coated gold nanoparticles (AuNP) are incorporated into conventional hydrophobic polymeric semiconductors like poly-3-hexylthiophene (P3HT), improving not only ionic but also electronic transport. The hydrophilic AuNPs modify P3HT crystallite orientation, shorten lamellar and π–π distances, and create pathways for ion penetration, as evidenced by GIWAXS and AFM studies. With 5 wt% AuNP loading, OECTs achieve µC* of 98 F cm−1 V−1 s−1, comparable to hydrophilic materials. The strategy also works for other polymer systems, offering a facile method to utilize hydrophobic materials in OECTs and boost their performance.

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) requires a matrix, and traditionally small organic matrices (SOMs) carrying acidic or basic functional groups are used. However, the analyte ionization via secondary processes in the gas-phase seems to be more important than primary processes. For conjugated polymeric matrices, an even more complicated picture emerges due to their apolar and aprotic nature, high molecular weight, and low tendency to desorb. Poly(3-dodecylthiophene-2,5-diyl) (P3DDT), a good matrix for low-molecular weight (LMW) analytes, does not give matrix-related peaks in the LMW area. Here, carboxylic acid (-COOH) side-chains are introduced via postpolymerization modification. The polymers are characterized by NMR, FT-IR, CV, MALDI MS, and, when possible, GPC. The electron withdrawing side-chains serve three functions; i) raising the ionization potential (IP), ii) improving the absorption maximum, and iii) acting as a source of protons. When measuring basic amines, this results in the occurrence of additional [Analyte + H+]+ signals compared to polymers without acidic groups, where only radical cations [Analyte]+• are detected. Similarly, estradiol and testosterone, compounds with high IPs, are not detected by polythiophenes without acidic groups, while P3DDT-COOH enables detection as protonated species.

Organic-hybrid particle-based materials are increasingly important in (opto)electronics, sensing, and catalysis due to their printability and stretchability as well as their potential for unique synergistic functional effects. However, these functional properties are often limited due to poor electronic coupling between the organic shell and the nanoparticle. N-heterocyclic carbenes (NHCs) belong to the most promising anchors to achieve electronic delocalization across the interface, as they form robust and highly conductive bonds with metals and offer a plethora of functionalization possibilities. Despite the outstanding potential of the conductive NHC-metal bond, synthetic challenges have so far limited its application to the improvement of colloidal stabilities, disregarding the potential of the conductive anchor. Here, NHC anchors are used to modify redox-active gold nanoparticles (AuNPs) with conjugated triphenylamines (TPA). The resulting AuNPs exhibit excellent thermal and redox stability benefiting from the robust NHC-gold bond. As electrochromic materials, the hybrid materials show pronounced color changes from red to dark green, a highly stable cycling stability (1000 cycles), and a fast response speed (5.6 s/2.1 s). Furthermore, TPA-NHC@AuNP exhibits an ionization potential of 5.3 eV and a distinct out-of-plane conductivity, making them a promising candidate for application as hole transport layers in optoelectronic devices.

Macromolecular materials play a pivotal role in (opto)electronic and energy storage applications. Achieving high performance materials necessitates a profound comprehension of the intricate interplay between macromolecular structures and (electronic)function. One illustrative case is the design of polymers tailored for electron transport as semiconductors or conductors, which often features an extended 𝜋-conjugated system, triggering a cascade of necessary design rules and limitations. The research into these structure-function interdependencies is highly dynamic and our understanding of them is constantly evolving, allowing us to continuously increase material performance and also to devise new applications. At the same time, new developments and emerging applications are expanding the spectrum of criteria used to evaluate material performance. The parameter space that must be considered now encompasses interactions with biological systems throughout and beyond the device’s lifespan, i.e., markers of biocompatibility and transience. Once again, understanding the structure–function relationships is crucial. This understanding becomes paramount, for instance, in achieving the delicate balance between ion permeability and electron transport for inter-facing with biological tissues, modulating the Young’s modulus of a polymeric semiconductor for wearables, or to include structurally weak points in the molecular system to facilitate controlled degradation or recycling. This special issue on “Macromolecular Structures for Electronics, Optoelectronics, and Energy Storage” features a collectionof 13 research papers and 3 review articles. These contributions delve into various facets of the relationship between macromolecular structure and function, collectively underscoring the essential nature of a comprehensive understanding of this interdependency in the pursuit for high performance materials. Examples are provided across the diverse fields of polymer synthesis, processing (including 3D techniques), controlled degradation, and application-driven investigations spanning photovoltaics, energy storage, wearable electronics and logic circuits

N-Heterocyclic carbenes are highly effective ligands for anchoring functional organic molecules to metal surfaces and nanoparticles, facilitating the formation of self-assembled monolayers. However, their adsorption on surface is difficult to predict and control, and there is an ongoing debate on the geometry of NHC derivatives on gold surfaces and on the role of gold adatoms. We present two single molecules based on a benzimidazole NHC, one equipped with a thiophene substituent, and the other ending with a Br atom. By low temperature scanning tunneling microscopy we show that both molecules adsorb planar on Au(111) and are chiral on the surface. Our results indicate that in both cases a complex between NHC and a gold adatom is formed. Upon voltage pulses with the STM tip, both complexes move excited by inelastic tunneling electrons. For the derivative with thiophene, we observe a stepwise 60° unidirectional rotation around the S atom. The direction of rotation is determined by both the chirality and the position of the applied pulse. On the contrary, the NHC derivative without thiophene moves laterally on the surface. Adsorption, binding to gold atoms, and motion are discussed with the support of density functional theory calculations and image simulations.

In the midst of the COVID-19 pandemic, adaptive solutions are needed to allow us to make fast decisions and take effective sanitation measures, e.g., the fast screening of large groups (employees, passengers, pupils, etc.). Although being reliable, most of the existing SARS-CoV-2 detection methods cannot be integrated into garments to be used on demand. Here, we report an organic field-effect transistor (OFET)-based biosensing device detecting of both SARS-CoV-2 antigens and anti-SARS-CoV-2 antibodies in less than 20 min. The biosensor was produced by functionalizing an intrinsically stretchable and semiconducting triblock copolymer (TBC) film either with the anti-S1 protein antibodies (S1 Abs) or receptor-binding domain (RBD) of the S1 protein, targeting CoV-2-specific RBDs and anti-S1 Abs, respectively. The obtained sensing platform is easy to realize due to the straightforward fabrication of the TBC film and the utilization of the reliable physical adsorption technique for the molecular immobilization. The device demonstrates a high sensitivity of about 19%/dec and a limit of detection (LOD) of 0.36 fg/mL for anti-SARS-Cov-2 antibodies and, at the same time, a sensitivity of 32%/dec and a LOD of 76.61 pg/mL for the virus antigen detection. The TBC used as active layer is soft, has a low modulus of 24 MPa, and can be stretched up to 90% with no crack formation of the film. The TBC is compatible with roll-to-roll printing, potentially enabling the fabrication of low-cost wearable or on-skin diagnostic platforms aiming at point-of-care concepts.

An innovative possibility to introduce additional functionality to organic field-effect transistors (OFETs) is to employ photochromic molecules, which undergo reversible isomerization under applied stimuli such as irradiation with specific wavelengths. As a result, the transistors not only can be switched on/off by the applied voltages, they can also be programmed by alternate triggers, such as light. Here, reversible switching of OFETs is presented by blending various dihydroazulene/vinylheptafulvene photoswitches into polythiophene-based conjugated polymers. In result, the transfer characteristics of the transistors are altered significantly through UV irradiation. In contrast to current literature on different photoswitches such as spiropyrans or diarylethenes, the backreaction is induced thermally and not via visible light irradiation and reproducibly yields the pristine transistor characteristics. This reversible switching upon alternating UV irradiation and thermal annealing is quantified by figures of merit such as the magnitude of drain current, threshold voltage, and subthreshold swing. Irradiating the devices with different doses of UV light shows that the magnitude of switching directly depends on the respective UV dose, hence enabling a multi-level electronic system. Furthermore, long-term cyclability over 100 steps of repeated UV light exposure and thermal annealing is demonstrated.

Stretchable semiconductors are vital for the development of emerging electronic biointerfaces. The physical blending of polymer semiconductors into elastomers presents a promising and straightforward method for creating stretchable films with high charge carrier mobilities. However, the understanding of the interplay between film morphology and the associated mechanical and electronic characteristics in blends is still limited. Especially, investigations into the blending behavior of more complex conjugated polymers, such as block copolymers, are lacking. In this study, we investigate the blending behavior of two semiconducting and stretchable triblock copolymers (TBCs). These copolymers comprise a middle block of poly(diketopyrrolopyrrole-co-thienothiophene) (PDPP-TT) and two outer blocks of poly(dimethylsiloxane) (PDMS) with different block-size ratios (85:15 and 40:60). The TBCs are blended into a crosslinked PDMS matrix. The resulting blends exhibit superior stretchability compared to the PDPP-TT homopolymer and retain their electric properties down to 40% PDPP-TT content in the blend. Increasing the PDMS block size inhibits macrophase separation and results in drastic decrease in charge carrier mobility, suggesting the necessity for macrophase separation within TBC/elastomer blends to maintain superior electric properties.

Exploring the limits of the microscopic reversibility principle, we investigated the interplay between thermal and electron tunneling excitations for the unidirectional rotation of a molecule-rotor on the Au(111) surface. We identified a range of moderate voltages and temperatures where heating the surface enhances the unidirectional rotational rate of a chemisorbed DMNI-P rotor. At higher voltage, inelastic tunneling effects dominate, while at higher temperature, the process becomes stochastic. At each electron transfer event during tunneling, the quantum mixing of ground and excited electronic states brings part of the surface thermal energy in the excited electronic states of the molecule-rotor. Thermal energy contributes therefore to the semiclassical unidirectional rotation without contradicting the microscopic reversibility principle.