Oxocarbon derivatives consisting of 4- and 5-membered rings, referred to as croconaine and squaraine dyes and regarded as closed-shell molecules, are found to have an intermediate open-shell character from the experimental results of 1H-NMR, ESR spectroscopy, SQUID magnetometric analysis, and X-ray crystallography. We employed two chalcogenopyrylium moieties with O and S chalcogen atoms as substitutions on oxocarbons. The singlet-triplet energy gaps (ΔE S-T) associated with the degree of diradical nature are smaller for croconaines than for squaraines and smaller for thiopyrylium than for pyrylium groups. The diradical nature impacts the electronic transition energy that decreased with a decreasing degree of diradical contribution. They exhibit substantial two-photon absorption in the region over 1000 nm. The diradical character y of the dye was determined experimentally from the observed one- and two-photon absorption peaks and the triplet energy level. The present finding provides new insight into diradicaloids with the contribution of non-Kekulé oxocarbon and also showcases the correlation between the electronic transition energy and their diradical character.
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