Polycyclic 1,2,5-chalcogenadiazole dyes: structural, optical, and redox properties in neutral and radical-ion states (chalcogen = S, Se)

Polycyclic 1,2,5-chalcogenadiazole dyes: structural, optical, and redox properties in neutral and radical-ion states (chalcogen = S, Se) Научная публикация

Журнал

Dyes and Pigments
ISSN: 1873-3743 , E-ISSN: 0143-7208

Вых. Данные

Год: 2025, Том: 242, Номер статьи : 112922, Страниц : DOI: 10.1016/j.dyepig.2025.112922

Авторы

Radiush Ekaterina A. ¹ , Korshunov Vladislav M. ^2,3 , Chulanova Elena A. ¹ , Konstantinova Lidia S. ⁴ , Ferulev Alexey I. ² , Irtegova Irina G. ¹ , Shundrina Inna K. ¹ , Frank Ekaterina A. ¹ , Semenov Nikolay A. ¹ , Taidakov Ilya V. ³ , Rakitin Oleg A. ⁴ , Shundrin Leonid A. ¹ , Zibarev Andrey V. ¹

Организации

1	Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russia
2	Bauman Moscow State Technical University, 105005 Moscow, Russia
3	Lebedev Physical Institute, Russian Academy of Sciences, 119991 Moscow, Russia
4	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia

Neutral M and radical-ion [M]·– and [M]·+ states of phenanthro- (1, 2)/dibenzoquinoxalino- (3, 4) fused 1,2,5-chalcogenadiazoles are studied; chalcogen = S (1, 3), Se (2, 4). Experimentally, 1–4 are characterized by simultaneous thermogravimetry – differential scanning calorimetry, spectroelectrochemistry and optical (UV–Vis–NIR/FL) spectroscopy, 2–4 by cyclic voltammetry (CV) for reduction and oxidation, and [M]·– by electron paramagnetic resonance ([M]·+ were not detected). Compounds 3, 4 and [M]·– (in the form of [K(18-crown-6)]+ salts; M = 1, 3) are characterized by X-ray diffraction (all are planar), and [M]·– (M = 1–4) by UV–Vis–NIR. Theoretically, M and [M]·– (M = 1–4) are specified by density functional theory (DFT) calculations. As compared with the archetypal 2,1,3-benzothiadiazole (5), in 1–4 the π-extension and replacement of S by Se jointly lead to increase of DFT adiabatic electron affinity (0.8 → 2.1 eV), decrease of the absolute values of CV potentials (−1.5 → −0.5 V), broadening and bathochromic shifts of UV–Vis (∼310 → ∼420 nm) and FL (∼380 → ∼470 nm) bands. DFT adiabatic ionization energy of 1–4 of ∼7.9 eV is invariant to their structure (5: 8.7 eV). FL spectra of 1–4 exhibit small Stokes shifts; and those of 2 and 3, vibronic structures. The estimated excited-state lifetime τ1 is ∼1 ns (ns) for 3 and 4, and ∼2 ns for 2, while long-time component τ2 is ∼9 ns for 2 and ∼7 ns for 3. The findings suggest that 1–4 are promising organic π-dyes/non-fullerene electron acceptors for small-molecule optoelectronics.

Radiush E.A. , Korshunov V.M. , Chulanova E.A. , Konstantinova L.S. , Ferulev A.I. , Irtegova I.G. , Shundrina I.K. , Frank E.A. , Semenov N.A. , Taidakov I.V. , Rakitin O.A. , Shundrin L.A. , Zibarev A.V.
Polycyclic 1,2,5-chalcogenadiazole dyes: structural, optical, and redox properties in neutral and radical-ion states (chalcogen = S, Se)
Dyes and Pigments. 2025. V.242. 112922 . DOI: 10.1016/j.dyepig.2025.112922 WOS Scopus OpenAlex

Web of science:	WOS:001509586500001
Scopus:	2-s2.0-105007599290
OpenAlex:	W4410942521

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Scopus	2
Web of science	2
OpenAlex	2