Strain‐Enabled Redox Chemistry of Naphthalene <i>Peri</i> ‐Dichalcogenides: Synthetic Strategies, Unusual Reactivity, Mechanistic Insights and Potential Applications

ABSTRACT Naphthalene peri‐dichalcogenides featuring sulfur, selenium, or tellurium at the 1,8‐positions constitute a privileged platform where enforced proximity of two heavy chalcogen centers raises donor ability, introduces strain, and enables through‐bond/through‐space communication. In this Review, we critically explore how these structural constraints give rise to a range of unusual reactivity patterns including rapid two‐ and multi‐electron redox processes and proton‐coupled electron‐transfer pathways that can trigger self‐redox behavior. Stepwise oxidation often leads to the formation of persistent radical cations, particularly in sulfur and selenium systems. In contrast, tellurium derivatives frequently access thermally robust dications, whose stability is enhanced by secondary or hypervalent interactions. We summarize the synthetic approaches used to access both open peri‐dichalcogenides substituent pairs and bridged naphtho[cd]dichalcogenoles, including peri‐directed metalation followed by elemental chalcogen transfer, stepwise substitution of peri‐dihalo aromatics, and oxidative coupling routes. Particular emphasis is placed on substituent patterns, suc