Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates.

A metal-free route for the synthesis of biarenes has been developed. The approach is based on the photoextrusion of a phosphate moiety occurring upon irradiation of biaryl- and triaryl phosphates. The reaction involves an exciplex as the intermediate and it is especially suitable for the preparation of electron-rich biarenes.

Organic Light-Emitting Transistors with Simultaneous Enhancement of Optical Power and External Quantum Efficiency via Conjugated Polar Polymer Interlayers.

Organic light-emitting transistors (OLETs) show the fascinating combination of electrical switching characteristics and light generation capability. However, to ensure an effective device operation, an efficient injection of charges into the emissive layer is required. The introduction of solution-processed conjugated polyelectrolyte (CPE) films at the emissive layer/electrode interface represents a promising strategy to improve the electron injection process by dipole formation. However, their use in optoelectronic devices also involves some limitations because of the ionic nature of CPEs. In this context, neutral conjugated polar polymers (CPPs) represent a valid alternative to CPEs because the conjugated backbones of CPPs are functionalized with polar nonionic side groups, thus avoiding ion-dependent drawbacks. By introducing a layer of polyfluorene-containing phosphonate groups underneath the metal electrodes, we here demonstrate a substantial improvement of the electron injection properties into the OLET-emissive layer and, accordingly, a more than 2-fold increased light power and a 5 times higher external quantum efficiency of p-type OLETs in comparison with reference devices without any interlayer. The great benefit of using a transparent glass substrate allowed to selectively investigate the morphological and photoluminescent characteristics of both CPE- and CPP-buried interlayers within complete OLETs by means of an optical scanning probe technique. This, together with a thorough optoelectronic characterization of the figures of merit of working light-emitting devices, allowed to disclose the origin of the improved optical performance of CPP-based devices as well as the operation mechanisms of the investigated interlayer in the corresponding OLETs.

Halogen-bonding-triggered supramolecular gel formation.

Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel ('co-gel') is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a 'tipping point' in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.