π-Extended S-Heterocyclic Naphthoquinodimethane with Dual Diradical and Dipolar Character.

The 2,6-naphthoquinodimethane (2,6-NQDM) containing -heterocyclic molecule was synthesized, and its dual open-shell diradical and dipolar characters were revealed via both experimental and theoretical studies. Unlike the shorter -quinodimethane (-QDM)-containing analogue , which possesses a closed-shell ground state ( = 0%) with small dipolar character, possesses enhanced dipolar character with a singlet diradical ground state ( = 23.3%) and a thermally accessible triplet excited state (Δ = -4.13 kcal/mol). Despite this, it displays good stability ( = 41days) under ambient air and light conditions due to its distinctive dipolar character and kinetic blocking of reactive sites.