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
1. [1]
  Irie M, Mohri M. Thermally irreversible photochromic systems—Reversible photocyclization of diarylethene derivatives[J]. J. Org. Chem., 1988,53(4):803-808. doi: 10.1021/jo00239a022
2. [2]
  Gilat S L, Kawasi S H, Lehn J M. Light-triggered molecular devices: Photochemical switching of optical and electrochemical properties in molecular wire type diarylethene species[J]. Chem. Eur. J., 1995,1(5):275-284. doi: 10.1002/chem.19950010504
3. [3]
  Kawasi S H, Gilat S. L, Ponsine R. A dual-mode molecular switching device: Bisphenolic diarylethenes with integrated photochromic and electrochromic properties[J]. Chem. Eur. J., 1995,1(5):285-293. doi: 10.1002/chem.19950010505
4. [4]
  Yamada T, Kobatake S, Muto K, Irie M. X-ray crystallographic study on single-crystalline photochromism of bis(2,5-dimethyl-3-thienyl)-perfluorocyclopentene[J]. J. Am. Chem. Soc., 2000,122(8):1589-1592. doi: 10.1021/ja993289x
5. [5]
  Higashiguchi K, Matsuda K, Irie M. Photochromic reaction of a fused dithienylethene: multicolor photochromism[J]. Angew. Chem. Int. Ed., 2003,42(30):3537-3540. doi: 10.1002/anie.200351751
6. [6]
  Kobatake S, Uchida K, Tsuchida E, Irie M. Single-crystalline photochromism of diarylethenes: Reactivity-structure relationship[J]. Chem. Commun., 2002(23):2804-2805. doi: 10.1039/B208419H
7. [7]
  Irie M, FukaminatoT , Matsuda K, Kobatake S. Photochromism of diarylethene molecules and crystals: Memories, switches, and actuators[J]. Chem. Rev., 2014,114(24):12174-12277. doi: 10.1021/cr500249p
8. [8]
  Ichikawa T, Morimoto M, Sotome H, Ito S, Miyasaka H, Irie M. Photochromism of diarylethene derivatives having benzophosphole and benzothiophene groups[J]. Dyes Pigment., 2016,126:186-193. doi: 10.1016/j.dyepig.2015.11.023
9. [9]
  Irie M. Diarylethenes for memories and switches[J]. Chem. Rev., 2000,100(5):1685-1716. doi: 10.1021/cr980069d
10. [10]
  Zhang J J, Tian H. The endeavor of diarylethenes: New structures, high performance, and bright future[J]. Adv. Opt. Mater., 2018,6(6)1701278. doi: 10.1002/adom.201701278
11. [11]
  Milek M, Heinemann F W, Khusniyarov M M. Spin crossover meets diarylethenes: Efficient photoswitching of magnetic properties in solution at room temperature[J]. Inorg. Chem., 2013,52(19):11585-11592. doi: 10.1021/ic401960x
12. [12]
  Vagin S I, Ott A K, Hoffmann S D, Lanzinger D, Rieger B. Synthesis and properties of (triptycenedicarboxylatio) zinc coordination networks[J]. Chem.-Eur. J., 2013,15(23):5845-5853.
13. [13]
  ZHENG C M, WANG T T, ZENG H P. Synthesis and photochromic properties of diarylethene-based porphyrin derivative and its metal complexes[J]. Chin. J. Org. Chem., 2012,32(4):719-726.
14. [14]
  Munakata M, Han J, Nabei A, Kuroda-Sowa T, Maekawa M, Suenaga Y, Gunjima N. Syntheses, structures and photochromism of two novel copper(Ⅱ) complexes with 1,2-bis(2'-methyl-5'-(2″-pyridyl)-3'-thienyl) perfluorocyclopentene[J]. Polyhedron, 2006,25(18):3519-3525. doi: 10.1016/j.poly.2006.06.045
15. [15]
  Munakata M, Han J, Nabei A, Kuroda-Sowa T, Maekawa M, Suenaga Y, Gunjima N. Reversible photochromism of novel silver(Ⅰ) coordination complexes with 1,2-bis(2'-methyl-5'-(2″-pyridyl)-3'-thienyl) perfluorocyclopentene in crystalline phase[J]. Inorg. Chim. Acta, 2006,359(13):4281-4288. doi: 10.1016/j.ica.2006.06.010
16. [16]
  Han J, Maekawa M, Suenaga Y, Ebisu H, Nabei A, Kuroda-Sowa T, Munakata M. Photochromism of novel metal coordination polymers with 1,2-bis(2'-methyl-5'-(carboxylic acid)-3'-thienyl)perfluorocyclopentene in crystalline phase[J]. Inorg. Chem., 2007,46(8):3313-3321. doi: 10.1021/ic0615168
17. [17]
  Han J, Chen H, Yu Z, Guo P. Photochromic 1,2-bis(2'-methyl-5'-(carboxylic acid)-3'-thienyl) perfluorocyclopentene and its Co(Ⅱ) coordination polymer[J]. Inorg. Chim. Acta, 2017,462:1-9. doi: 10.1016/j.ica.2017.03.005
18. [18]
  Munakata M, Han J, Maekawa M, Suenaga Y, Kuroda-Sowa T, Nabei A, Ebisu H. A MLCT-switched copper(Ⅱ) coordination polymer with 1,2-bis(2'-methyl-5'-(4″-pyridyl)-3'-thienyl)perfluorocyclopentene in crystalline phase[J]. Inorg. Chim. Acta, 2007,360(8):2792-2796. doi: 10.1016/j.ica.2006.12.026
19. [19]
  Han J, Konaka H, Kuroda-Sowa T, Maekawa M, Suenaga Y, Isihara H, Munakata M. Syntheses and structures of photochromic molybdenum(Ⅱ) and rhodium(Ⅱ) complexes with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl) ethene[J]. Inorg. Chim. Acta, 2006,359(1):99-108. doi: 10.1016/j.ica.2005.08.023
20. [20]
  Han J, Li S, Yu Z, Chen H, Zang Y, Wang Q J. A photochromic AgBF₄ complex with cis-1,2-dicyano-1,2-bis(2', 4', 5'-trimethyl-3'-thienyl)ethene: Synthesis, structure and photochromism[J]. Inorg. Chim. Acta, 2017,464:11-17. doi: 10.1016/j.ica.2017.04.039
21. [21]
  Liu G, Tu Q D, Zhang Q, Fan C B, Yang T S. 1,2-Bis[5-(4-cyanophenyl)-2-methyl-3-thienyl]-3,3,4,4,5,5-hexafluorocyclopentene: A photochromic diarylethene compound[J]. Acta Crystallogr. Sect. E, 2008,E64:O938-U2809.
22. [22]
  Han J, Li Q, Yu Z, Quan C Y, Liu X, Han J C. Light-driven coordination anions-directed regulation of chromism in three metal complexes assembled by cyano-equipped dithienylethene ligand[J]. Inorg. Chim. Acta, 2020,509119666. doi: 10.1016/j.ica.2020.119666
23. [23]
  Cromer D T, Waer J T, International tables for X-ray crystallography: Vol. Ⅳ. Birmingham: The Kynoch Press, 1974.
24. [24]
  Sheldrick G M. Crystal structure refinement with SHELXL[J]. Acta Crystallogr. Sect. C, 2015,C71:3-8.
25. [25]
  Yamaguchi T, Nomiyama K, Isayama M, Irie M. Reversible diastereoselective photocyclization of diarylethenes in a bulk amorphous state[J]. Adv. Mater., 2004,16(7):643-645. doi: 10.1002/adma.200305815
26. [26]
  Yamaguchi T, Uchida K, Irie M. Asymmetric photocyclization of diarylethene derivatives[J]. J. Am. Chem. Soc., 1997,119(26):6066-6071. doi: 10.1021/ja970200j
27. [27]
  Kodani T, Matsuda K, Yamada T, Kobatake S, Irie M. Reversible diastereoselective photocyclization of a diarylethene in a single-crystalline phase[J]. J. Am. Chem. Soc., 2000,122(40):9631-9637. doi: 10.1021/ja001350o
28. [28]
  Yamamoto S, Matsuda K, Irie M. Absolute asymmetric photocyclization of a photochromic diarylethene derivative in single crystals[J]. Angew. Chem. Int. Ed., 2003,42(14):1636-1639. doi: 10.1002/anie.200250417
29. [29]
  De Jong J J D, Lucas L N, Hania R, Pugzlys A, Kellogg R M, Feringa B L, Duppen K, van Esch J H. Photochromic properties of perhydro- and perfluorodithienylcyclopentene molecular switches[J]. Eur. J. Org. Chem., 2003(10):1887-1893.
30. [30]
  Castagna R, Nardone V, Pariani G, Biancoc A. The interplay of soft-hard substituents in photochromic diarylethenes[J]. J. Photochem. Photobiol. A: Chem., 2016,325:45-54. doi: 10.1016/j.jphotochem.2016.04.001
31. [31]
  Tsai F C, Chang C C, Liu C L, Chen W C, Jenekhe S A. New thiophene-linked conjugated poly(azomethine)s: Theoretical electronic structure, synthesis, and properties[J]. Macromolecules, 2005,38(5):1958-1966. doi: 10.1021/ma048112o
32. [32]
  Tsivgoulis G M, Lehn J M. Photoswitched and functionalized oligothiophenes: Synthesis and photochemical and electrochemical properties[J]. Chem.-Eur. J., 1996,2(11):1399-1406. doi: 10.1002/chem.19960021112
33. [33]
  Perrier A, Maurel F, Aubard J. Theoretical investigation of the substituent effect on the electronic and optical properties of photochromic dithienylethene derivatives[J]. J. Photochem. Photobiol. A: Chem., 2007,189(2/3):167-176.
1. [1]
  Zhaodong WANG . In situ synthesis, crystal structure, and magnetic characterization of a trinuclear copper complex based on a multi-substituted imidazo[1,5-a]pyrazine scaffold. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 597-604. doi: 10.11862/CJIC.20240268
2. [2]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
3. [3]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
4. [4]
  Huirong LIU , Hao XU , Dunru ZHU , Junyong ZHANG , Chunhua GONG , Jingli XIE . Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1368-1376. doi: 10.11862/CJIC.20240066
5. [5]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
6. [6]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
7. [7]
  Peng Meng , Qian-Cheng Luo , Aidan Brock , Xiaodong Wang , Mahboobeh Shahbazi , Aaron Micallef , John McMurtrie , Dongchen Qi , Yan-Zhen Zheng , Jingsan Xu . Molar ratio induced crystal transformation from coordination complex to coordination polymers. Chinese Chemical Letters, 2024, 35(4): 108542-. doi: 10.1016/j.cclet.2023.108542
8. [8]
  Chao Ma , Cong Lin , Jian Li . MicroED as a powerful technique for the structure determination of complex porous materials. Chinese Journal of Structural Chemistry, 2024, 43(3): 100209-100209. doi: 10.1016/j.cjsc.2023.100209
9. [9]
  Yinling HOU , Jia JI , Hong YU , Xiaoyun BIAN , Xiaofen GUAN , Jing QIU , Shuyi REN , Ming FANG . A rhombic Dy₄-based complex showing remarkable single-molecule magnet behavior. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 605-612. doi: 10.11862/CJIC.20240251
10. [10]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
11. [11]
  Mengjuan Sun , Muye Zhou , Yifang Xiao , Hailei Tang , Jinhua Chen , Ruitao Zhang , Chunjiayu Li , Qi Ya , Qian Chen , Jiasheng Tu , Qiyue Wang , Chunmeng Sun . Reversibly size-switchable polyion complex micelles for antiangiogenic cancer therapy. Chinese Chemical Letters, 2024, 35(7): 109110-. doi: 10.1016/j.cclet.2023.109110
12. [12]
  Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi . Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand. Chinese Chemical Letters, 2024, 35(7): 109292-. doi: 10.1016/j.cclet.2023.109292
13. [13]
  Jingwen Zhao , Jianpu Tang , Zhen Cui , Limin Liu , Dayong Yang , Chi Yao . A DNA micro-complex containing polyaptamer for exosome separation and wound healing. Chinese Chemical Letters, 2024, 35(9): 109303-. doi: 10.1016/j.cclet.2023.109303
14. [14]
  Ya-Ping Liu , Zhi-Rong Gui , Zhen-Wen Zhang , Sai-Kang Wang , Wei Lang , Yanzhu Liu , Qian-Yong Cao . A phenylphenthiazide anchored Tb(Ⅲ)-cyclen complex for fluorescent turn-on sensing of ClO⁻. Chinese Chemical Letters, 2025, 36(2): 109769-. doi: 10.1016/j.cclet.2024.109769
15. [15]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
16. [16]
  Fengyu Zhang , Yali Liang , Zhangran Ye , Lei Deng , Yunna Guo , Ping Qiu , Peng Jia , Qiaobao Zhang , Liqiang Zhang . Enhanced electrochemical performance of nanoscale single crystal NMC811 modification by coating LiNbO₃. Chinese Chemical Letters, 2024, 35(5): 108655-. doi: 10.1016/j.cclet.2023.108655
17. [17]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051
18. [18]
  Zhenfei Tang , Yunwu Zhang , Zhiyuan Yang , Haifeng Yuan , Tong Wu , Yue Li , Guixiang Zhang , Xingzhi Wang , Bin Chang , Dehui Sun , Hong Liu , Lili Zhao , Weijia Zhou . Iron-doping regulated light absorption and active sites in LiTaO₃ single crystal for photocatalytic nitrogen reduction. Chinese Chemical Letters, 2025, 36(3): 110107-. doi: 10.1016/j.cclet.2024.110107
19. [19]
  Xiaofen GUAN , Yating LIU , Jia LI , Yiwen HU , Haiyuan DING , Yuanjing SHI , Zhiqiang WANG , Wenmin WANG . Synthesis, crystal structure, and DNA-binding of binuclear lanthanide complexes based on a multidentate Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2486-2496. doi: 10.11862/CJIC.20240122
20. [20]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(687)
HTML views(103)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142