The field of organic electronics has been prolific in the last couple of years, leading to the design and synthesis of several molecular semiconductors presenting a mobility in excess of 10 cm2 V−1 s−1. However, it is also started to recently falter, as a result of doubtful mobility extractions and reduced industrial interest. This critical review addresses the community of chemists and materials scientists to share with it a critical analysis of the best performing molecular semiconductors and of the inherent charge transport physics that takes place in them. The goal is to inspire chemists and materials scientists and to give them hope that the field of molecular semiconductors for logic operations is not engaged into a dead end. To the contrary, it offers plenty of research opportunities in materials chemistry.

The development of systems capable of responding to environmental changes, such as humidity, requires the design and assembly of highly sensitive and efficiently transducing elements. Such a challenge can be mastered only by disentangling the role played by each component of the responsive system, thus ultimately achieving high performance by optimizing the synergistic contribution of all functional elements. Here, we designed and synthesized a novel [1]benzothieno [3,2-b][1]benzothiophene derivative equipped with hydrophilic oligoethylene glycol lateral chains (OEG-BTBT) that can electrically transduce subtle changes in ambient humidity with high current ratios (>10 4 ) at low voltages (2 V), reaching state-of-the-art performance. Multiscale structural, spectroscopical, and electrical characterizations were employed to elucidate the role of each device constituent, viz., the active material's BTBT core and OEG side chains, and the device interfaces. While the BTBT molecular core promotes the self-assembly of (semi)conducting crystalline films, its OEG side chains are prone to adsorb ambient moisture. These chains act as hotspots for hydrogen bonding with atmospheric water molecules that locally dissociate when a bias voltage is applied, resulting in a mixed electronic/protonic long-range conduction throughout the film. Due to the OEG-BTBT molecules' orientation with respect to the surface and structural defects within the film, water molecules can access the humidity-sensitive sites of the SiO 2 substrate surface, whose hydrophilicity can be tuned for an improved device response. The synergistic chemical engineering of materials and interfaces is thus key for designing highly sensitive humidity-responsive electrical devices whose mechanism relies on the interplay of electron and proton transport.

This work is focused on a polymorphic and crystallographic study of a novel p-type organic semiconductor 2,7-bis(2-(2-methoxyethoxy)ethoxy)benzo[b]benzo [4,5]thieno [2,3-d]thiophene (OEG-BTBT). The well-known BTBT core is functionalized by eight-atom-long oligoethylene glycol side chains. Our results demonstrate the discovery of three crystal forms of the OEG-BTBT molecule, namely, Form I, Form II, and Form III, in different experimental conditions. Crystal structures of Form I and Form III are reported, while only unit cell indexing of Form II could be determined. Form I and Form II are enantiotropically related, and Form II is stable at temperatures higher than 127 °C. The kinetics of transformation to Form II was studied by the Avrami equation. Form III is a solvate crystal form which is rarely observed in the field of organic electronics, and upon release of dichloromethane, it converts to Form I. Furthermore, we studied the mechanical properties of the Form I crystals, which exhibit plastic bending upon applying mechanical stress in the [100] direction. This distinct mechanical behavior is rationalized by the slip layer topology, the intermolecular interactions energies from energy frameworks, and the Hirshfeld surface analysis.

The discovery of new polymorphs opens unique applications for molecular materials, as the physical properties are predominantly influenced by the crystal structure type. Deposition of molecules at surfaces offers a...

No abstract