Three-State Switching of an Anthracene Extended Bis-thiaxanthylidene with a Highly Stable Diradical State.

A multistable molecular switching system based on an anthracene-extended bis-thiaxanthylidene with three individually addressable states that can be interconverted by electrochemical, thermal, and photochemical reactions is reported. Besides reversible switching between an open-shell diradical- and a closed-shell electronic configuration, our findings include a third dicationic state and control by multiple actuators. This dicationic state with an orthogonal conformation can be switched electrochemically with the neutral open-shell triplet state with orthogonal conformation, which was characterized by EPR. The remarkably stable diradical shows kinetic stability as a result of a significant activation barrier for isomerization to a more stable neutral closed-shell folded geometry. We ascribe this activation barrier of ΔG⧧(293 K) = 25.7 kcal mol-1 to steric hindrance in the fjord region of the overcrowded alkene structure. The folded closed-shell state can be converted back to the diradical state by irradiation with 385 nm. The folded state can also be oxidized to the dicationic state. These types of molecules with multiple switchable states and in particular stable diradicals show great potential in the design of new functional materials such as memory devices, logic gates, and OFETs.

Predicting the substituent effects in the optical and electrochemical properties of N,N'-substituted isoindigos.

Isoindigo, the structural isomer of the well-known dye indigo, has seen a major revival recently because of the increasing interest of its use as a potential drug core structure and for the development of organic photovoltaic materials. Highly beneficial for diverse applications are its facile synthesis, straightforward functionalisation and the broad absorption band in the visible range. Moreover, its intrinsic electron deficiency renders isoindigo a promising acceptor structure in bulk heterojunction architectures. Here we present new insights into the substituent effects of N-functionalised isoindigos, developing a reliable and fast in silico screening approach of a library of compounds. Using experimental UV-Vis and electrochemical data increased the accuracy of the TD-DFT method employed. This procedure allowed us to accurately predict the optical and electrochemical properties of N-functionalised isoindigos and the elucidation of the relationship between substituent effects and electronic properties.

Fast synthesis and redox switching of di- and tetra-substituted bisthioxanthylidene overcrowded alkenes.

A rapid and efficient method for the synthesis of overcrowded alkenes using (trimethylsilyl)diazomethane provides a range of substituted bisthioxanthylidenes. We show large conformational redox switching from folded to orthogonal states, which tolerates many substitution patterns. The facile access to bisthioxanthylidene switches with the potential for further functionalization, in combination with the reliable redox chemistry, provides major opportunities for the design of electrochemically responsive systems.

Palladium-Catalyzed C(sp(3))-C(sp(2)) Cross-Coupling of (Trimethylsilyl)methyllithium with (Hetero)Aryl Halides.

The palladium-catalyzed direct cross-coupling of a range of organic chlorides and bromides with the bifunctional C(sp(3))-(trimethylsilyl)methyllithium reagent is reported. The use of Pd-PEPPSI-IPent as the catalyst allows for the preparation of structurally diverse and synthetically versatile benzyl- and allylsilanes in high yields under mild conditions (room temperature) with short reaction times.