Citation: Shuang Zhao, Fei Jia, Kaibei Zhan, Rui-Xi Wang, Pengfei Tan, Lin Shen, Li-Ming Wu, Ling Chen. Amino substitution strategy achieves significant blue shift while preserving high optical anisotropy: A₂(H₃C₃N₄S₂)₂•H₂O (A =NH₄, K, Rb, Cs)[J]. Chinese Chemical Letters, ;2026, 37(3): 110625. doi: 10.1016/j.cclet.2024.110625 shu

Amino substitution strategy achieves significant blue shift while preserving high optical anisotropy: A₂(H₃C₃N₄S₂)₂•H₂O (A =NH₄, K, Rb, Cs)

Shuang Zhao ^a ,
Fei Jia ^a ,
Kaibei Zhan ^{b, c} ,
Rui-Xi Wang ^b ,
Pengfei Tan ^d ,
Lin Shen ^e ,
Li-Ming Wu ^{a, b, *,} ,
Ling Chen ^{a, b, *,}

a.
Center for Advanced Materials Research, Beijing Normal University, Zhuhai 519087, China
b.
Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University, Beijing 100875, China
c.
South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
d.
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-sen University, Guangzhou 510006, China
e.
Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China

wlm@bnu.edu.cn

chenl@bnu.edu.cn

Received Date: 5 October 2024
Revised Date: 1 November 2024
Accepted Date: 7 November 2024
Available Online: 10 November 2024

Figures(4)

The trithiocyanurate, (H₂C₃N₃S₃)^-, exhibits a strong optical anisotropy but has a small HOMO-LUMO gap, limiting its application to the higher energy wavelength ranges. Herein, by applying an amino substitution strategy, we report that 2-amino-4,6-dimercapto-S-triazine, (H₃C₃N₄S₂)^-, generates a series new compound: A₂(H₂C₃N₄S₂)₂•H₂O (NH₄, Ⅰ; K−Cs, Ⅱ−Ⅳ). Compound Ⅰ crystallizes in P2₁/n, while compounds Ⅱ–Ⅳ crystallize in P1. Their experimental optical band gaps (E_g) range from 3.52 eV to 3.65 eV, corresponding to a blue shift of 30~60 nm compared to those of the trithiocyanuric containing systems. Moreover, the birefringence of all compounds ranges from 0.440 to 0.510, indicating strong anisotropy. Notably, compound Ⅰ (E_g = 3.65 eV, \begin{document}$ \Delta n_{cal.}^{\max}$\end{document} = 0.510, \begin{document}$ \Delta n_{o b v.}^{(0 \overline{1} \overline{1})} $\end{document} = 0.413 at 546 nm) exhibits one of the largest birefringence values among materials with an absorption cutoff edge shorter than 330 nm. The work introduces a new candidate group for preparing optical materials with a desired wide band gap and strong optical anisotropy.
- Amino substitution strategy,
- Planar π-conjugated group,
- Optical anisotropy,
- Birefringence,
- Ultraviolet crystal
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Amino substitution strategy achieves significant blue shift while preserving high optical anisotropy: A2(H3C3N4S2)2•H2O (A =NH4, K, Rb, Cs)

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通讯作者: 陈斌, bchen63@163.com

Amino substitution strategy achieves significant blue shift while preserving high optical anisotropy: A₂(H₃C₃N₄S₂)₂•H₂O (A =NH₄, K, Rb, Cs)