3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electron-withdrawing groupsand their analogs for organic electronics. Remarkably efficient tuning the energy levels in flatconjugated polymers

A novel, facile and efficient one-pot, microwave-assisted method of synthesis allowing an access to a new series of 3,4-phenylenedioxythiophene derivatives with electron-withdrawing groups at the benzene ring (EWG-PheDOT) and their analogs (with an expanded side π-system or with heteroaromatic rings, ArDOT) by the reaction of 2,5-dialkoxycarbonyl-3,4-dihydroxythiophenes with electrophilic aromatic/heteroaromatic compounds in dipolar aprotic solvents has been described. Its applicability over a wide range of novel functionalized ArDOTs as promising building blocks for organic electronic materials has been demonstrated. The structures of selected ArDOTs have been determined by single-crystal X-ray diffraction. The electronic structure of conjugated polymers p[ArDOTs] based on synthesized novel thiophene monomers has been studied theoretically by the DFT PBC/B3LYP/6-31G(d) method. The performed calculations reveal that while the side functional groups are formally not in conjugation with the polymer main chain, they have an unprecedentedly strong effect on the HOMO/LUMO energy levels of conjugated polymers, allowing their efficient tuning by over the range of 1.6 eV. In contrast to that, the energy gaps of the polymers are almost unaffected by such functionalizations and vary within a range of only ≤0.05 eV. Computational predictions have been successfully confirmed in experiments: cyclic voltammetry shows a strong anodic shift of p-doping for the electron-withdrawing CF3 group functionalized polymer p[4CF3-PheDOT] relative to the unsubstituted p[PheDOT] polymer (by 0.55 V; DFT predicted the decrease of the HOMO by 0.58 eV), while very similar Vis-NIR absorption spectra for both polymers in the undoped state indicate that their optical energy gaps nearly coincide (ΔEg < 0.04 eV). © 2018 The Royal Society of Chemistry

Delocalized, Asynchronous, Closed-Loop Discovery of Organic Laser Emitters

Contemporary materials discovery requires intricate sequences of synthesis, formulation and characterization that often span multiple locations with specialized expertise or instrumentation. To accelerate these workflows, we present a cloud-based strategy that enables delocalized and asynchronous design–make–test–analyze cycles. We showcase this approach through the exploration of molecular gain materials for organic solid-state lasers as a frontier application in molecular optoelectronics. Distributed robotic synthesis and in-line property characterization, orchestrated by a cloud-based AI experiment planner, resulted in the discovery of 21 new state-of-the-art materials. Automated gram-scale synthesis ultimately allowed for the verification of best-in-class stimulated emission in a thin-film device. Demonstrating the asynchronous integration of five laboratories across the globe, this workflow provides a blueprint for delocalizing – and democratizing – scientific discovery