Citation: Zhong YU, Yu-Xue WANG, Jia-Cai HAN, Jing HAN. A closed-ring dithienylethene and its Ag(Ⅰ) complex: Syntheses, structures, and reversible photochromism[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(5): 947-958. doi: 10.11862/CJIC.2023.065 shu

A closed-ring dithienylethene and its Ag(Ⅰ) complex: Syntheses, structures, and reversible photochromism

Zhong YU ¹ ,
Yu-Xue WANG ² ,
Jia-Cai HAN ² ,
Jing HAN ^2,,

1.
Department of Applied Chemistry, Xi′an University of Technology, Xi′an 710054, China
2.
Department of Materials Physics and Chemistry, Xi′an University of Technology, Xi′an 710048, China

Corresponding author: Jing HAN, hanj@xaut.edu.cn
Received Date: 21 November 2022
Revised Date: 14 March 2023

Figures(10)

A new cyano-equipped dithienylethene in closed-ring form (L_c) was first isolated and structurally characterized by IR, ¹H NMR, and X-ray single-crystal diffraction. It showed an interesting racemic mixture of R,R and S,S enantiomer pairs evidencing the structural transformation from 1,3,5-hexatriene to cyclohexadiene in the photochemical conrotatory cyclization. Followed UV-Vis spectral investigations exhibited its reversible photochromism in both THF solution and solid state with the maximum absorption wavelength of 607 nm observed in the visible band. The photo-isomerization kinetics of the compound indicated a first-order process for photo-reversion and zeroth-order for photo-cyclization. The compound was further used as a ligand to self-assemble with Ag(CF₃SO₃) resulting in complex 1. Its structure was characterized by elemental analysis, IR, ¹H NMR, and ESI-MS. Complex 1 demonstrated reversible photochromism in the solid state with the same λ_max as the closed-ring ligand. Unlike the complex derived from the open-ring ligand, Ag(Ⅰ) ions coordination with the closed-ring ligand doesn′t modify the absorption due to the restricted free rotation of the thienyl rings in the rigid configuration of the closed-ring ligand. In comparison with the open-ring ligand, 1 displayed a faster photo-isomerization rate corresponding to the smaller band gap determined by cyclic voltammetry.
- dithienylethene,
- closed-ring isomer,
- photochromism,
- single crystal structure,
- complex
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