Issue 8, 2023

Unveiling a new aspect of oxocarbons: open-shell character of 4- and 5-membered oxocarbon derivatives showing near-infrared absorption

Abstract

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 (ΔES–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.

Graphical abstract: Unveiling a new aspect of oxocarbons: open-shell character of 4- and 5-membered oxocarbon derivatives showing near-infrared absorption

Supplementary files

Article information

Article type
Edge Article
Submitted
01 12 2022
Accepted
14 1 2023
First published
16 1 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 1978-1985

Unveiling a new aspect of oxocarbons: open-shell character of 4- and 5-membered oxocarbon derivatives showing near-infrared absorption

T. Maeda, T. Oka, D. Sakamaki, H. Fujiwara, N. Suzuki, S. Yagi, T. Konishi and K. Kamada, Chem. Sci., 2023, 14, 1978 DOI: 10.1039/D2SC06612B

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