Rational Design of Stimuli‐Responsive Inorganic 2D Materials via Molecular Engineering: Toward Molecule‐Programmable Nanoelectronics

Abstract The ability of electronic devices to act as switches makes digital information processing possible. Succeeding graphene, emerging inorganic 2D materials (i2DMs) have been identified as alternative 2D materials to harbor a variety of active molecular components to move the current silicon‐based semiconductor technology forward to a post‐Moore era focused on molecule‐based information processing components. In this regard, i2DMs benefits are not only for their prominent physiochemical properties (e.g., the existence of bandgap), but also for their high surface‐to‐volume ratio rich in reactive sites. Nonetheless, since this field is still in an early stage, having knowledge of both i) the different strategies for molecularly functionalizing the current library of i2DMs, and ii) the different types of active molecular components is a sine qua non condition for a rational design of stimuli‐responsive i2DMs capable of performing logical operations at the molecular level. Consequently, this Review provides a comprehensive tutorial for covalently anchoring ad hoc molecular components—as active units triggered by different external inputs—onto pivotal i2DMs to assess their role in the expanding field of molecule‐programmable nanoelectronics for electrically monitoring bistable molecular switches. Limitations, challenges, and future perspectives of this emerging field which crosses materials chemistry with computation are critically discussed.