Citation: Longfei MA, Fang SI, Congjie PAN, Xinhua WANG. Synthesis and crystal structure of extended tetrathiafulvalene derivatives and cupric bromide charge transfer complexes[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(6): 1229-1236. doi: 10.11862/CJIC.20250355 shu

Synthesis and crystal structure of extended tetrathiafulvalene derivatives and cupric bromide charge transfer complexes

Longfei MA ^1,, ,
Fang SI ¹ ,
Congjie PAN ² ,
Xinhua WANG ^1,,

1.
Department of Criminal Science and Technology, Henan Police College, Zhengzhou 450046, China
2.
School of Pharmacy, Henan University of Chinese Medicine, Zhengzhou 450046, China

Corresponding author: Longfei MA, malongfei@hnp.edu.cn Xinhua WANG, gyxxwxh@163.com
Received Date: 26 November 2025
Revised Date: 17 April 2026

Figures(8)

Three charge-transfer complexes, (T1)[Cu₂Br₆]·2THF, (T2)[Cu₂Br₆]·2THF, and (T3)[Cu₂Br₆], have been prepared via diffusion methods comprising extended tetrathiafulvalene (exTTF) derivatives C₁₄H₈(C₃S₂(S-R)₂)₂ [R=phenyl (T1), thiophen-2-yl (T2), pyridin-2-yl (T3)] and CuBr₂. Crystallographic studies indicate that T1²⁺, T2²⁺, and T3²⁺ present different molecular configurations, while [Cu₂Br₆]^2- anions exhibit two different coordination configurations (planar and octahedral), which further lead to different crystal packing structures of the three complexes. Notably, altering the peripheral aryl groups of exTTF derivatives can effectively regulate the anion configuration, and compounds T1-T3 can flexibly adjust their own configurations to match the anion structure and crystal packing requirements, thereby providing a solid basis for designing tunable supramolecular materials with potential optoelectronic applications.
- tetrathiafulvalene derivative,
- cupric bromide,
- charge transfer complexes,
- crystal structure
1. [1]
  WUDL F, SMITH G M, HUFNAGEL E J. Bis-1, 3-dithiolium chloride: An unusually stable organic radical cation[J]. J. Chem. Soc. D‒Chem. Commun., 1970, 21: 1453-1454
2. [2]
  FRÈRE P, SKABARA P J. Salts of extended tetrathiafulvalene analogues: Relationships between molecular structure, electrochemical properties and solid state organisation[J]. Chem. Soc. Rev., 2005, 34(1): 69-98 doi: 10.1039/B316392J
3. [3]
  CANEVET D, SALLÈ M, ZHANG G X, ZHANG D Q, ZHU D B. Tetrathiafulvalene(TTF) derivatives: Key building-blocks for switchable processes[J]. Chem. Commun., 2009, (17): 2245-2269 doi: 10.1039/b818607n
4. [4]
  DING H M, LI Y H, HU H, SUN Y M, WANG J G, WANG C X, WANG C, ZHANG G X, WANG B S, XU W, ZHANG D Q. A tetrathiafulvalene-based electroactive covalent organic framework[J]. Chem. ‒Eur. J., 2014, 20(45): 14614-14618 doi: 10.1002/chem.201405330
5. [5]
  YIN W Y, WENG Y G, REN Z H, ZHANG Z R, ZHU Q Y, DAI J. Tetrathiafulvalene-based double metal lead iodides: Structures and electrical properties[J]. Dalton Trans., 2021, 50(23): 8120-8126
6. [6]
  LI J L, WEN Y H, WANG L J, LI X, XIAO X W. Photocurrent response properties of 2, 6-bis(3′-pyridyl)-tetrathiafulvalene based Zn/Co coordination polymer[J]. Chinese J. Inorg. Chem., 2022, 38(4): 745-751
7. [7]
  COTELLE Y, HARDOUIN-LEROUGE M, LEMASSON E, MORILLE Y, CANEVET D, LEGOUPY S, HUDHOMME P. An original self- assembly using a tetrathiafulvalene-based molecular clip for the recognition of fullerene C₆₀[J]. Chem. Commun., 2020, 56: 3077-3080 doi: 10.1039/C9CC09633G
8. [8]
  CALBO J, DE JUAN A, ARAGÓ J, VILLALVA J, MARTÍN N, PÉREZ E M, ORTI E. Understanding the affinity of bis-exTTF macrocyclic receptors towards fullerene recognition[J]. Phys. Chem. Chem. Phys., 2019, 21: 11670-11675 doi: 10.1039/C9CP01735F
9. [9]
  PÉREZ E M, SÁNCHEZ L, FERNÁNDEZ G, MARTÍN N. ExTTF as a building block for fullerene receptors. Unexpected solvent‑ dependent positive homotropic cooperativity[J]. J. Am. Chem. Soc., 2006, 128: 7172-7173 doi: 10.1021/ja0621389
10. [10]
  CHANG X M, XU Y Z, DELIUS VON M. Recent advances in supramolecular fullerene chemistry[J]. Chem. Soc. Rev., 2024, 53: 47-83
11. [11]
  BERA S, DAS S, MELLE-FRANCO M, MATEO-ALONSO A. An organic molecular nanobarrel that hosts and solubilizes C₆₀[J]. Angew. Chem. ‒Int. Edit., 2023, 62(5): e202216540 doi: 10.1002/anie.202216540
12. [12]
  HU L, QIN J, ZHU R M, LI Y Z, ZUO J L, YOU X Z. Syntheses, characterization, and properties of functionalized 9, 10-bis(1, 3-dithiol-2-ylidene)-9, 10-dihydroanthracene derivatives and tricarbonylrhenium(Ⅱ) complexes[J]. Eur. J. Inorg. Chem., 2012: 2494-2501
13. [13]
  YOSHIMURA A, MISAKI Y. Periphery modification of tetrathiafulvalenes: Recent development and applications[J]. Chem. Rec., 2021, 21: 3520-3531
14. [14]
  DEKHTIARENKO M, ALLAIN M, CARRÉ V, AUBRIET F, VOITENKO Z, SALLÉ M, GOEB S. Comparing the self-assembly processes of two redox-active exTTF-based regioisomer ligands[J]. New J. Chem., 2021, 45: 21015-21019 doi: 10.1039/D1NJ04555E
15. [15]
  GOEB S, SALLÉ M. Electron-rich coordination receptors based on tetrathiafulvalene derivatives: Controlling the host-guest binding[J]. Accounts Chem. Res., 2021, 54(4): 1043-1055 doi: 10.1021/acs.accounts.0c00828
16. [16]
  MA L F, PENG H L, LU X F, LIU L, SHAO X F. Building up 1-D, 2-D, and 3-D polyiodide frameworks by finely tuning the size of aryls on Ar-S-TTF in the charge-transfer(CT) complexes of Ar-S-TTFs and iodine[J]. Chin. J. Chem., 2018, 36(9): 845-850
17. [17]
  MA L F, SUN J B, LU X F, ZHANG S X, QI H, LIU L, SHAO Y L, SHAO X F. Copper ion salts of arylthiotetrathiafulvalenes: Synthesis, structure diversity and magnetic properties[J]. Beilstein J. Org. Chem., 2015, 11: 850-859
18. [18]
  SUN J B, LU X F, SHAO J F, LI X X, ZHANG S X, WANG B L, ZHAO J L, SHAO Y L, FANG R, WANG Z H, YU W, SHAO X F. Molecular and crystal structure diversity, and physical properties of tetrathiafulvalene derivatives substituted with various aryl groups through sulfur bridges[J]. Chem. ‒Eur. J., 2013, 19: 12517-12525
19. [19]
  LU X F, SUN J B, LIU Y, SHAO J F, MA L F, ZHANG S X, ZHAO J L, SHAO Y L, ZHANG H L, WANG Z H, SHAO X F. Decorating tetrathiafulvalene (TTF) with fluorinated phenyls through sulfur bridges: Facile synthesis, properties, and aggregation through fluorine interactions[J]. Chem. ‒Eur. J., 2014, 20: 9650-9656
20. [20]
  MA L F, ZHU Z H, HUANG X B. Synthesis and crystal structure of arylthiotetrathiafulvalenes and cupric bromide charge transfer complexes[J]. Chinese J. Inorg. Chem., 2022, 38(5): 821-828 doi: 10.11862/CJIC.2022.086
21. [21]
  MA L F, WU WU L X, LU X F. Synthesis, structures, and physical properties of exTTF substituted with aryl groups through sulfur bridges and the electron transfers with C₆₀[J]. Eur. J. Org. Chem., 2025, 28: e202401193
22. [22]
  PÉREZ I, LIU S G, MARTÍN N, ECHEGOYEN L. Synthesis and properties of conjugated hybrid tetrathiafulvalene dimers[J]. J. Org. Chem., 2000, 65: 3796-3803
23. [23]
  BRUNETTI F G, LOPEZ J L, ATIENZA C, MARTÍN N. π-Extended TTF: A versatile molecule for organic electronics[J]. J. Mater. Chem., 2012, 22: 4188-4205
24. [24]
  BRYCE M R, MOORE A J, HASAN M, ASHWELL G J, FRASER A T, CLEGG W, HURSTHOUSE M B, KARAULOV A I. Electrical and magnetic properties and X-ray structure of a highly conductive 4∶1 complex of tetracyanoquinodimethane and a tetrathiafulvalene derivative[J]. Angew. Chem. ‒Int. Edit., 1990, 29: 1450-1452
25. [25]
  SUN J B, LU X F, SHAO J F, CUI Z L, SHAO Y, JIANG G Y, YU W, SHAO X F. Straightforward access to aryl-substituted/fused 1, 3-dithiole-2-chalcogenones by Cu-catalyzed C—S coupling between aryl iodides and zinc-thiolate complex (TBA)₂[Zn(DMIT)₂][J]. RSC Adv., 2013, 3(26): 10193-10196
1. [1]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
2. [2]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
3. [3]
  Weina Wang , Fengyi Liu , Wenliang Wang . “Extracting Commonality, Delving into Typicals, Deriving Individuality”: Constructing a Knowledge Graph of Crystal Structures. University Chemistry, 2024, 39(3): 36-42. doi: 10.3866/PKU.DXHX202308029
4. [4]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
5. [5]
  Hongjie SHEN , Haozhe MIAO , Yuhe YANG , Yinghua LI , Deguang HUANG , Xiaofeng ZHANG . Synthesis, crystal structure, and fluorescence properties of two Cu(Ⅰ) complexes based on pyridyl ligand. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 855-863. doi: 10.11862/CJIC.20250009
6. [6]
  Chengyan XU , Jiangnan YU , Yu LI , Xizhen PAN , Yinlin HOU , Wenmin WANG . Synthesis, structure, and bioactivity of a Ho₄ complex bridged by azide group. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1453-1462. doi: 10.11862/CJIC.20260033
7. [7]
  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
8. [8]
  Hexing SONG , Zan SUN . Synthesis, crystal structure, Hirshfeld surface analysis, and fluorescent sensing for Fe³⁺ of an Mn(Ⅱ) complex based on 1-naphthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 885-892. doi: 10.11862/CJIC.20240402
9. [9]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
10. [10]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395
11. [11]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
12. [12]
  Yuxin CHEN , Yanni LING , Yuqing YAO , Keyi WANG , Linna LI , Xin ZHANG , Qin WANG , Hongdao LI , Wenmin WANG . Construction, structures, and interaction with DNA of two Sm^Ⅲ₄ complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1141-1150. doi: 10.11862/CJIC.20240258
13. [13]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
14. [14]
  Jia JI , Tengqi YAO , Wenqian DENG , Wenjing SHI , Xuan LÜ , Lin TIAN , Xiaoyan XIN , Yinling HOU . Structures, antibacterial activities, and interactions with DNA of two nickel complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 78-86. doi: 10.11862/CJIC.20250141
15. [15]
  Wenjuan SHI , Yuxuan LEI , Lei HOU , Yaoyu WANG . Synthesis, structure, and luminescence properties of trinucluear Cu(Ⅰ)-pyrazole complexes containing different substituent groups. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 543-550. doi: 10.11862/CJIC.20250270
16. [16]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
17. [17]
  Lifang HE , Wenjie TANG , Yaoze LUO , Mingsheng LIANG , Jianxin TANG , Yuxuan WU , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two dialkyltin complexes constructed based on 2, 2′-bipyridin-6, 6′-dicarboxylic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1601-1609. doi: 10.11862/CJIC.20250012
18. [18]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
19. [19]
  Yan Liu , Yuexiang Zhu , Luhua Lai . Introduction to Blended and Small-Class Teaching in Structural Chemistry: Exploring the Structure and Properties of Crystals. University Chemistry, 2024, 39(3): 1-4. doi: 10.3866/PKU.DXHX202306084
20. [20]
  Junqiao Zhuo , Xinchen Huang , Qi Wang . Symbol Representation of the Packing-Filling Model of the Crystal Structure and Its Application. University Chemistry, 2024, 39(3): 70-77. doi: 10.3866/PKU.DXHX202311100

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(655)
HTML views(154)

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