WOS: QUARTILE 1 

В журнале  Dyes and Pigments ( IF 4,1) по результатам работы, выполненной совместно с коллегами из Института физики им. Лебедева, Института органической химии им. Зелинского и МГТУ им. Баумана, опубликована статья, соавторами которой является сотрудники Института: к.х.н. Е.А. Радюш (нс, ЛГетС), к.х.н. Е.А. Чуланова , к.х.н. И.Г. Иртегова (снс, ЛЭАСМ), к.х.н. И.К. Шундрина (снс, ЛЭАСМ), Е.А. Франк, к.х.н. Н.А. Семёнов, д.х.н. Л.А. Шундрин (завлаб ЛЭАСМ) и д.х.н. А.В. Зибарев (г.н.с., ЛГетС)

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

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

Dyes and Pigments, Volume 242, November 2025, 112922

 DOI: 10.1016/j.dyepig.2025.112922

Abstract

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.

Graphical abstract

Due to thermal, structural, optical, and redox properties in neutral and radical-anion states, synthetically easily-available polycyclic 1,2,5-chalcogenadiazoles (chalcogen = S, Se) are promising π-dyes/non-fullerene electron acceptors for organic optoelectronics.

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