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.