A Compact Tetrathiafulvalene-Benzothiadiazole Dyad and Its Highly Symmetrical Charge-Transfer Salt: Ordered Donor π-Stacks Closely Bound to Their Acceptors

A compact and planar donor–acceptor molecule 1 comprising tetrathiafulvalene (TTF) and benzothiadiazole (BTD) units has been synthesised and experimentally characterised by structural, optical, and electrochemical methods. Solution-processed and thermally evaporated thin films of 1 have also been explored as active materials in organic field-effect transistors (OFETs). For these devices, hole field-effect mobilities of μFE=(1.3±0.5)×10−3 and (2.7±0.4)×10−3 cm2 V s−1 were determined for the solution-processed and thermally evaporated thin films, respectively. An intense intramolecular charge-transfer (ICT) transition at around 495 nm dominates the optical absorption spectrum of the neutral dyad, which also shows a weak emission from its ICT state. The iodine-induced oxidation of 1 leads to a partially oxidised crystalline charge-transfer (CT) salt {(1)2I3}, and eventually also to a fully oxidised compound {1I3}⋅1/2I2. Single crystals of the former CT compound, exhibiting a highly symmetrical crystal structure, reveal a fairly good room temperature electrical conductivity of the order of 2 S cm−1. The one-dimensional spin system bears compactly bonded BTD acceptors (spatial localisation of the LUMO) along its ridge.

Inverse and symmetrical voice: On languages with two transitive constructions

In voice and alignment typology, a categorical distinction is generally made between inverse systems on the one hand and symmetrical voice systems on the other. A major reason for distinguishing between these two types is the assumption that inverse systems are governed by a hierarchy involving grammatical, semantic, and ontological criteria, while symmetrical voice systems are based on discourse-pragmatic factors. However, the two types also have several important properties in common, in particular the fact that they have more than one nonderived transitive construction. Based on data from three native languages of South America, we show that the line between the two types is not always easy to draw, and that features of the inverse type can coexist with those of the symmetrical-voice type in the same language.