Research demonstrates how ion pairing modulates diradical character in π‐electronic systems, suggesting tunable properties.
A quinonoidal dipyrrolyldiketone catecholate‐boron complex, with two pyrrole‐quinonemethide moieties bridged by a six‐membered cross‐conjugated unit, was synthesized to modulate the diradical character of the dianion formed upon deprotonation. The dianionic species exhibited near‐infrared absorption and electron spin resonance (ESR) signals, confirming the diradical properties. Variable‐temperature (VT) ESR spectra suggest the thermal excitation from the ground‐state singlet diradical to the triplet diradical, providing singlet–triplet energy gaps modulated by coexisting cations and bridging boron moieties.
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Kobayashi et al. (2025) studied this question.
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