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

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2025-06-02 DOI:10.1016/j.dyepig.2025.112922

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

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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.

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多环1,2,5-硫代二唑染料：中性和自由基离子状态下的结构、光学和氧化还原性能（硫= S, Se）

研究了菲-(1,2)/二苯并喹啉-(3,4)熔融1,2,5-硫代二唑的中性M态和自由基离子[M]·-态和[M]·+态；chalgen = S (1,3), Se（2,4）。实验中，1-4采用同步热重法-差示扫描量热法、光谱电化学和光学（UV-Vis-NIR /FL）光谱进行表征，2-4采用循环伏安法（CV）进行还原和氧化，[M]·-采用电子顺磁共振（未检测到[M]·+）。化合物3,4和[M]·-（以[K(18-冠-6)]+盐的形式）；M = 1,3)用x射线衍射（均为平面）和紫外-可见-近红外（UV-Vis-NIR）表征[M]·- (M = 1 - 4)。理论上，M和[M]·- (M = 1-4)是由密度泛函理论（DFT）计算指定的。与原型2,1,3-苯并噻唑(5)相比，在1 - 4中π扩展和S被Se取代共同导致DFT绝热电子亲和力增加（0.8→2.1 eV）， CV电位绝对值降低（- 1.5→- 0.5 V）， UV-Vis（~ 310→~ 420 nm）和FL（~ 380→~ 470 nm）波段变宽和显色偏移。DFT绝热电离能1-4 （~ 7.9 eV）与它们的结构无关（5:7 .7 eV）。1-4的FL光谱表现出小的Stokes位移；2号和3号是振动结构。估计激发态寿命τ1在3和4中为~ 1 ns (ns)，在2中为~ 2 ns，而长时间分量τ2在2中为~ 9 ns，在3中为~ 7 ns。结果表明，1-4是小分子光电子学中很有前途的有机π染料/非富勒烯电子受体。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.