Deprotonation-Induced and Ion-Pairing-Modulated Diradical Properties of Partially Conjugated Pyrrole-Quinone Conjunction.

uinoidal molecules based on diyrrolyldiketone oron complexes (s), in which pyrrole units were connected by a partially conjugated system as a singlet spin coupler, were synthesized. , which was stabilized by the introduction of a benzo unit at the pyrrole β-positions, formed a closed-shell tautomer conformation that showed near-infrared absorption. The deprotonated species, monoanion and dianion , showing over 1000 nm absorption, were formed by the addition of bases, providing ion pairs in combination with countercations. Diradical properties were observed in , whose hyperfine coupling constants were modulated by ion-pairing with π-electronic and aliphatic cations, demonstrating cation-dependent diradical properties. VT NMR and ESR along with a theoretical study revealed that the singlet diradical was more stable than the triplet diradical.