Substituted 2,1,3-benzothiadiazole (BTD) is a widely used electron acceptor unit for functional organic semiconductors. Difluorination or annulation on the 5,6-position of the benzene ring is among the most adapted chemical modifications to tune the electronic properties, though each sees its own limitations in regulating the frontier orbital levels. Herein, a hitherto unreported 5,6-annulated BTD acceptor, denoted as ssBTD, is designed and synthesized by incorporating an electron-withdrawing 2-(1,3-dithiol-2-ylidene)malononitrile moiety via aromatic nucleophilic substitution of the 5,6-difluoroBTD (ffBTD) precursor. Unlike the other reported BTD annulation strategies, this modification leads to the simultaneous decrease in both frontier orbital energies, a welcoming feature for photovoltaic applications. Incorporation of ssBTD into conjugated polymers results in materials boasting broad light absorption, dramatic solvatochromic and thermochromic responses (>100 nm shift and a band gap difference of ∼0.28 eV), and improved crystallinity in the solid state. Such physical properties are in accordance with the combined electron-withdrawing effect and significantly increased polarity associated with the ssBTD unit, as revealed by detailed theoretical studies. Furthermore, the thiolated ssBTD imbues the polymer with ambipolar charge transport property, in contrast to the ffBTD-based polymer, which transports holes only. While the low mobilities (10^-4 to 10^-5 cm² V^-1 s^-1) could be further optimized, detailed studies validate that the thioannulated BTD is a versatile electron-accepting unit for the design of functional stimuli-responsive optoelectronic materials.

Hydroxyl radical (OH) is a key oxidant that triggers atmospheric oxidation chemistry in both gas and aqueous phases. The current understanding of its aqueous sources is mainly based on known bulk (photo)chemical processes, uptake from gaseous OH, or related to interfacial O3 and NO3 radical-driven chemistry. Here, we present experimental evidence that OH radicals are spontaneously produced at the air-water interface of aqueous droplets in the dark and the absence of known precursors, possibly due to the strong electric field that forms at such interfaces. The measured OH production rates in atmospherically relevant droplets are comparable to or significantly higher than those from known aqueous bulk sources, especially in the dark. As aqueous droplets are ubiquitous in the troposphere, this interfacial source of OH radicals should significantly impact atmospheric multiphase oxidation chemistry, with substantial implications on air quality, climate, and health.