Citation: Zhang Shangxi, Shao Xiangfeng. Flexible TTF Derivatives: Synthesis, Structure and Self-assembly[J]. Acta Chimica Sinica, ;2018, 76(7): 531-536. doi: 10.6023/A18040157 shu

Flexible TTF Derivatives: Synthesis, Structure and Self-assembly

Zhang Shangxi ^a,, ,
Shao Xiangfeng ^b

a.
School of Science, Nanchang Institute of Technology, Nanchang 330099
b.
State Key Laboratory of Applied Organic Chemistry, Lanzhou University Lanzhou 730000

Corresponding author: Zhang Shangxi, shangxi_1997@163.com
Received Date: 18 April 2018
Available Online: 29 July 2018
Fund Project: the National Natural Science Foundation of China 21603093the National Natural Science Foundation of China 21372111the Research and Technology foundation of Jiangxi Provincial Education Department GJJ151112the National Natural Science Foundation of China 21702090Project supported by the Research and Technology foundation of Jiangxi Provincial Education Department (No. GJJ151112) and the National Natural Science Foundation of China (Nos. 21702090, 21603093, 21372111)

Figures(9)

Organic electron donors with planar configuration, moderate redox potential and favorable flexibility are the foundation of the molecular material science and self-assembly chemistry. A series of TTF derivatives (TTF1~TTF8) with well molecule flexibility have been synthesized employing a copper-mediated C—S coupling reaction of 1, 2-diiodophenyl groups and a zinc-thiolate complex, (TBA)₂[Zn(DMIT)₂] (TBA=tetrabutyl ammonium, DMIT=1, 3-dithiole-2-thione-4, 5-dithiolate) as the key step. The physicochemical properties and crystal structures of these TTFs are fully investigated by UV/Vis absorption spectra, cyclic voltammetry, single crystal X-ray diffraction. The ethylenedioxy/ethylenedithio group and sulfur attached phenyl groups lead to unusual properties of TTFs. In comparison with TTF5~TTF8 containing ethylenedithio groups, TTF1~TTF4 substituted by ethylenedioxy groups exhibit stronger absorbance, due to the different electronegative of oxygen and sulfur atom. In addition the absorbance is reducing progressively as the electron donating ability of the respective aryl groups increasing. By introducing fused aryls, the first half redox potential (E_1/2¹) used to estimate the electrochemical stability of different organic electron donors of the TTF derivatives are much higher than that of BEDT-TTF and TTF itself. The aryls ensure the stability of TTF-core via dispersing its electrons. By hot recrystallization or slowly evaporating the solvent, single crystals of eight TTFs suitable for single-crystal X-ray diffraction measurement were obtained. All these TTF derivatives adopt boat conformation with various dihedral angles between the central C₂S₄ plane with the terminal C₂O₂ and C₂S₂ plane of the TTF framework. Complicated aryls leads to larger dihedral angles. TTF5~TTF8 with ethylenedithio groups have more dominant curving configuration with respect to TTF1~TTF4 functionalized by ethylenedioxy groups. Additionally, the stereo-hindrance effects due to the fused phenyl groups prolong the distance from one molecule to another. As a typical example of crystal structure of TTF4, the two methoxy groups make the distance much longer than that in TTF1. Furthermore, the flexible TTFs exhibit unique behavior on self-assembling when the C—S bond vibrate upon and down the TTF-skeleton plane. Single crystals of the complex (TTF4)(C₆₀) are obtained via slowly evaporating chlorobenzene at room temperature after the mixture was heated and refluxed for five minutes. The dihedral angles of TTF4 enlarges to some extent from 24.30° in monomer to 30.17° in complex. Two electron donor molecules produced a cavity and a C₆₀ molecule filled the cavity with C—C and C—S contacts.
- organic electro donor,
- tetrathiafulvalene (TTF),
- photoelectric stability,
- flexibility,
- self-assembly
1. [1]
  Wudl, F.; Smith, G. M.; Hufnagel, E. J. J. Chem. Soc. D Chem. Commun. 1970, 1453.
2. [2]
  (a) Xiao, X.; Xu, W.; Zhang, D.; Xu, H.; Lu, H.; Zhu, D. J. Mater. Chem. 2005, 26, 2557; (b) Canavet, D.; Sall, M.; Zhang, G.; Zhang, D.; Zhu, D. Chem. Commun. 2009, 2245, and references therein.
3. [3]
  For typical examples of the use of TTF derivatives in sensors, see: (a) Hansen, T. K.; Jø rgensen, T.; Stein, P. C.; Becher, J. J. Org. Chem. 1992, 57, 6403; (b) Jø rgensen, T.; Hansen, T. K.; Becher, J. Chem. Soc. Rev. 1994, 23, 41; (c) Le Derf, F.; Mazari, M.; Mercier, N.; Levillain, E.; Gorgues, A.; Sallé, M.; Richomme, P.; Becher, J.; Garín, J.; Orduna, J. Chem. Commun. 1999, 1417; (d) Johnston, B.; Goldenberg, L. M.; Bryce, M. R.; Kataky, R. J. Chem. Soc. Perkin Trans. 2 2000, 189; (e) Herranz, M. A.; Colonna, B.; Echegoyen, L. Proc. Natl. Acad. Sci. USA 2002, 99, 5040; (f) Li, X.; Zhang, G.; Ma, H.; Zhang, D.; Li, J.; Zhu, D. J. Am. Chem. Soc. 2004, 126, 11543; (g) Lyskawa, J.; Le Derf, F.; Levillain, E.; Mazari, M.; Sallé, M.; Dubois, L.; Viel, P.; Bureau, C.; Palacin, S. J. Am. Chem. Soc. 2004, 126, 12194; (h) Zhang, G.; Li, X.; Ma, H.; Zhang, D.; Li, J.; Zhu, D. Chem. Commun. 2004, 2072; (i) Nielsen, K. A.; Cho, W. S.; Jeppesen, J. O.; Lynch, V. M.; Becher, J.; Sessler, J. L. J. Am. Chem. Soc. 2004, 126, 16296; (j) Wang, Z.; Zhang, D.; Zhu, D. J. Org. Chem. 2005, 70, 5729; (k) Nielsen, K. A.; Cho, W. S.; Lyskawa, J.; Levillain, E.; Lynch, V. M.; Sessler, J. L.; Jeppesen, J. O. J. Am. Chem. Soc. 2006, 128, 2444; (l) Zhao, Y. P.; Wu, L. Z.; Si, G.; Liu, Y.; Xue, H.; Zhang, L. P.; Tung, C. H. J. Org. Chem. 2007, 72, 3632.
4. [4]
  (a) de Lucas, A. I.; Martán, N.; Sínchez, L.; Seoane, C.; Andreu, R.; Garán, J.; Orduna, J.; Alcalá, R.; Villacampa, B. Tetrahedron 1998, 54, 4655; (b) González, M.; Martín, N.; Segura, J. L.; Garín, J.; Orduna, J. Tetrahedron Lett. 1998, 39, 3269; (c) González, M.; Martín, N.; Segura, J. L.; Seoane, C.; Garín, J.; Orduna, J.; Alcalá, R.; Sánchez, C.; Villacampa, B. Tetrahedron Lett. 1999, 40, 8599; (d) Garín, J.; Ordura, J.; Andreu, R. Recent Res. Dev. Org. Chem. 2001, 5, 77, and references therein.
5. [5]
  (a) Mas-Torrent, M.; Durkut, M.; Hadley, P.; Ribas, X.; Rovira, C. J. Am. Chem. Soc. 2004, 126, 984; (b) Nishida, J.; Ando, S.; Yamaguchi, J.; Itaka, K.; Koinuma, H.; Tada, H.; Tokito, S.; Yamashita, Y. J. Am. Chem. Soc. 2005, 127, 10142; (c) Nishida, J.; Kumaki, D.; Tokito, S.; Yamashita, Y. J. Am. Chem. Soc. 2006, 128, 9598; (d) Gao, X.; Wang, Y.; Yang, X.; Liu, Y.; Qiu, W.; Wu, W.; Zhang, H.; Qi, T.; Liu, Y.; Lu, K.; Du, C.; Shuai, Z.; Yu, G.; Zhu, D. Adv. Mater. 2007, 19, 3037; (e) Gao, X.; Wu, W.; Liu, Y.; Jiao, S.; Qiu, W.; Wang, L.; Zhu, D. J. Mater. Chem. 2007, 17, 736; (f) Yang, G.; Di, C.; Zhang, G.; Zhang, J.; Xiang, J.; Zhang, D.; Zhu, D. Adv. Funct. Mater. 2013, 23, 1671; (g) Yamashita, Y. Sci. Technol. Adv. Mater. 2009, 10, 024313; (h) Wu, W.; Liu, Y.; Zhu, D. Chem. Soc. Rev. 2010, 39, 1489; (i) Mas-Torrent, M.; Rovira, C. Chem. Rev. 2011, 111, 4833; (j) Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Chem. Rev. 2012, 112, 2208.
6. [6]
  (a) Aviram, A.; Ratner, M. A. Chem. Phys. Lett. 1974, 29, 277; (b) Metzger, R. M. J. Mater. Chem. 1999, 9, 2027; (c) Scheib, S.; Cava, M. P.; Baldwin, J. W.; Metzger, R. M. J. Org. Chem. 1998, 63, 1198; (d) Ho, G.; Heath, J. R.; Kondratenko, M.; Perepichka, D. F.; Arseneault, K.; Pézolet, M.; Bryce, M. R. Chem. Eur. J. 2005, 11, 2914.
7. [7]
  (a) Xiao, X.; Hayashi, T.; Fujiwara, H.; Sugimoto, T.; Noguchi, S.; Weng, Y.; Yoshino, H.; Murata, K.; Katari, H. J. Am. Chem. Soc. 2007, 129, 12618; (b) Shao, X.; Nakano, Y.; Sakata, M.; Yamochi, H.; Yoshida, Y.; Maesato, M.; Uruichi, M.; Yakushi, K.; Murata, T.; Otsuka, A.; Saito, G.; Koshihara, S.; Tanaka, K. Chem. Mater. 2008, 20, 7551.
8. [8]
  (a) Liao, H.; Wang, H.; Ding, H.; Meng, X.; Xu, H.; Wang, B.; Ai, X.; Wang, C. J. Mater. Chem. A 2016, 4, 7416; (b) Liao, H.; Ding, H.; Li, B.; Ai, X.; Wang, C. J. Mater. Chem. A 2014, 2, 8854. (c) Xu, F.; Jin, S.; Zhong, H.; Wu, D.; Yang, X.; Chen, X.; Wei, H.; Fu, R.; Jiang, D. Sci. Rep. 2015, 5, 8225.
9. [9]
  (a) Berridge, R.; Skabara, P. J.; Pozo-Gonzalo, C.; Kanibolotsky, A.; Lohr, J.; McDouall, J. J. W.; McInnes, E. J. L.; Wolowska, J.; Winder, C.; Sariciftci, N. S.; Harrington, R. W.; Clegg, W. J. Phys. Chem. B 2006, 110, 3140; (b) Martín, N.; Sánchez, L.; Herranz, M. A.; Illescas, B.; Guldi, D. M. Acc. Chem. Res. 2007, 40, 1015, and references therein.
10. [10]
  Zhang, J.; Jiang, M.; Xing, L.; Qin, K.; Liu, T.; Zhou, J.; Si, W.; Cui, H.; Zhou, S. Chin. J. Chem. 2016, 34, 46. doi: 10.1002/cjoc.201500656
11. [11]
  (a) Mitamura, Y.; Yorimitsu, H.; Oshima, K.; Osuka, A. Chem. Sci. 2011, 2, 2017; (b) Lincke, K.; Frellsen, A. F.; Parker, C. R.; Bond, A. D.; Hammerich, O.; Nielsen, M. B. Angew. Chem. 2012, 124, 6203. Angew. Chem. Int. Ed. 2012, 51, 6099; (c) Ueno, R.; Fujino, D.; Yorimitsu, H.; Osuka, A. Chem. Eur. J. 2013, 19, 7156.
12. [12]
  Zhao, B.; Tao, J.; Chen, X.; Zhu, W. Chin. J. Org. Chem. 2017, 37, 1964. doi: 10.6023/cjoc201702002
13. [13]
  (a) Kim, C.; Lee, S. J.; Lee, H. Chem. Mater. 2003, 15, 3638; (b) Stellacci, F.; Bauer, C. A.; Meyer-Friedrichsen, T. J. Am. Chem. Soc. 2003, 125, 328.
14. [14]
  (a) Kryschenko, Y. K.; Seidel, S. R.; Muddiman, D. C. J. Am. Chem. Soc. 2003, 125, 9647; (b) Zhang, Y.; Li, J.; Chen, J.; Su, Q.; Deng, W.; Nishiura, M.; Imamoto, T.; Wu, X.; Wang, Q. Inorg. Chem. 2000, 39, 2330.
15. [15]
  (a) Narita, M.; Pittman, C. U. Synthesis 1976, 8, 489; (b) Krief, A. Tetrahedron 1986, 42, 1204; (c) Fabre, J. M. Chem. Rev. 2004, 104, 5133.
16. [16]
  Sun, J.; Lu, X.; Shao, J.; Cui, Z.; Shao, Y.; Jiang, G.; Yu, W.; Shao, X. RSC Adv. 2013, 3, 10193. doi: 10.1039/c3ra41349g
17. [17]
  (a) Horiuchi, S.; Yamochi, H.; Saito, G.; Sakaguchi, K.; Kusunoki, M. J. Am. Chem. Soc. 1996, 118, 8604; (b) Collet, M.; Guerin, L.; Uchida, N.; Fukuya, S.; Shimoda, H.; Ishiguro, T.; Matsuda, K.; Hasegawa, T.; Ota, A.; Yamochi, H.; Saito, G.; Tazaki, R.; Adachi, S.; koshihara, S. Science 2005, 307, 86.
18. [18]
  CCDC number: 1829987-1829990, 1830217, 1830219-1830221.
19. [19]
  Bondi, A. J. Phys. Chem. 1964, 68, 441. doi: 10.1021/j100785a001
1. [1]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
2. [2]
  Ruoxi Sun , Yiqian Xu , Shaoru Rong , Chunmiao Han , Hui Xu . The Enchanting Collision of Light and Time Magic: Exploring the Footprints of Long Afterglow Lifetime. University Chemistry, 2024, 39(5): 90-97. doi: 10.3866/PKU.DXHX202310001
3. [3]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
4. [4]
  Renqing Lü , Shutao Wang , Fang Wang , Guoping Shen . Computational Chemistry Aided Organic Chemistry Teaching: A Case of Comparison of Basicity and Stability of Diazine Isomers. University Chemistry, 2025, 40(3): 76-82. doi: 10.12461/PKU.DXHX202404119
5. [5]
  Xuewei BA , Cheng CHENG , Huaikang ZHANG , Deqing ZHANG , Shuhua LI . Preparation and luminescent performance of Sr_1-xZrSi₂O₇∶xDy³⁺ phosphor with high thermal stability. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 357-364. doi: 10.11862/CJIC.20240096
6. [6]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
7. [7]
  Wenjian Zhang , Mengxin Fan , Wenwen Fei , Wei Bai . Cultivation of Critical Thinking Ability: Based on RAFT Polymerization-Induced Self-Assembly. University Chemistry, 2025, 40(4): 108-112. doi: 10.12461/PKU.DXHX202406099
8. [8]
  Shitao Fu , Jianming Zhang , Cancan Cao , Zhihui Wang , Chaoran Qin , Jian Zhang , Hui Xiong . Study on the Stability of Purple Cabbage Pigment. University Chemistry, 2024, 39(4): 367-372. doi: 10.3866/PKU.DXHX202401059
9. [9]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
10. [10]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
11. [11]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
12. [12]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
13. [13]
  Jiaxi Xu , Yuan Ma . Influence of Hyperconjugation on the Stability and Stable Conformation of Ethane, Hydrazine, and Hydrogen Peroxide. University Chemistry, 2024, 39(11): 374-377. doi: 10.3866/PKU.DXHX202402049
14. [14]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
15. [15]
  Zeyi Yan , Ruitao Liu , Xinyu Qi , Yuxiang Zhang , Lulu Sun , Xiangyuan Li , Anchao Feng . Exploration of Suspension Polymerization: Preparation and Fluorescence Stability of Perovskite Polystyrene Microbeads. University Chemistry, 2025, 40(4): 72-79. doi: 10.12461/PKU.DXHX202405110
16. [16]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
17. [17]
  Hong CAI , Jiewen WU , Jingyun LI , Lixian CHEN , Siqi XIAO , Dan LI . Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 114-122. doi: 10.11862/CJIC.20240382
18. [18]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
19. [19]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
20. [20]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393

Get Citation

PDF

XML

Metrics

PDF Downloads(17)
Abstract views(1802)
HTML views(403)

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