Citation: Long-Fei MA, Zhao-Hui ZHU, Xiao-Bo HUANG. Synthesis and Crystal Structure of Arylthiotetrathiafulvalenes and Cupric Bromide Charge Transfer Complexes[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(5): 821-828. doi: 10.11862/CJIC.2022.086 shu

Synthesis and Crystal Structure of Arylthiotetrathiafulvalenes and Cupric Bromide Charge Transfer Complexes

Department of Criminal Science and Technology, Henan Police College, Zhengzhou 450046, China

Corresponding author: Long-Fei MA, malongfei@hnp.edu.cn
Received Date: 3 November 2021
Revised Date: 15 February 2022

Figures(6)

Four charge-transfer complexes, (1^+·)(Cu₂Br₆)_0.5, (2^+·)(Cu₂Br₆)_0.5, (3^+·)(Cu₂Br₆)_0.5 and (4^+·)(CuBr₂), have been prepared via diffusion methods comprising arylthio-substituted tetrathiafulvalene derivatives 1-4 and CuBr₂. Crystal-lographic studies indicate that the anions in the complexes, which are derived from CuBr₂, show diverse configura-tions including octahedral (CuⅡ₂Br ₆)^2-and linear (CuⅠBr₂)^-. The plane of the outer four Br atoms and the plane of the central quadrilateral on(CuⅡ₂Br₆)^2-have a different dihedral angle. Compounds 1-4 show radical cation and the cen-tral framework of compounds 1-4 are nearly planar in the complexes. The stacking structure and anionic configura-tion of the charge transfer complexes can be effectively regulated by regulating the substitution positions and sizes of halogen atoms on the aryl groups. CCDC: 2119456, (1^+·)(Cu₂Br₆)_0.5;2119457, (2^+·)(Cu₂Br₆)_0.5;2119458, (3^+·)(Cu₂Br₆)_0.5;2119459, (4^+·)(CuBr₂).
- tetrathiafulvalene,
- cupric bromide,
- crystal structure,
- charge transfer complexes
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]
  Ferraris J, Cowan D O, Walatka V, Perlstein J H. Electron Transfer in a New Highly Conducting Donor -Acceptor Complex[J]. J. Am. Chem. Soc., 1973,95(3):948-949. doi: 10.1021/ja00784a066
3. [3]
  Jérome D, Mazaud A, Ribault M, Bechgaard K. Superconductivity in a Synthetic Organic Conductor (TMTSF)₂PF₆[J]. J. Physique Lett, 1980,41(4):95-98. doi: 10.1051/jphyslet:0198000410409500
4. [4]
  Bryce M R. Current Trends in Tetrathiafulvalene Chemistry: Towards Increased Dimensionality[J]. J. Mater. Chem., 1995,5(10):1481-1496. doi: 10.1039/jm9950501481
5. [5]
  Garín J. The Reactivity of Tetrathia -and Tetraselenafulvalenes//Katritzky A R. Advances in Heterocyclic Chemistry: Vol. 66. San Diego: Academic Press, 1995: 249-304
6. [6]
  Bryce M R. Tetrathiafulvalenes as π-Electron Donors for Intramolecular Charge-Transfer Materials[J]. Adv. Mater., 1999,11:11-23. doi: 10.1002/(SICI)1521-4095(199901)11:1<11::AID-ADMA11>3.0.CO;2-3
7. [7]
  Frère P, Skabara P J. Salts of Extended Tetrathiafulvalene Analogues: Relationships between Molecular Structure, Electrochemical Proper-ties and Solid State Organisation[J]. Chem. Soc. Rev., 2005,34(1):69-98. doi: 10.1039/B316392J
8. [8]
  Canevet D, Sallé M, Zhang G X, Zhang D Q, Zhu D B. Tetrathiafulva-lene (TTF) Derivatives: Key Building-Blocks for Switchable Processes[J]. Chem. Commun, 2009(17):2245-2269. doi: 10.1039/b818607n
9. [9]
  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
10. [10]
  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. doi: 10.1039/D1DT00631B
11. [11]
  XIE J Z, WANG D P, MA J P, WANG H Y, ZUO J L. Iron Com-plex Based on π-Conjugated 4-Tetrathiafulvalene-2, 6-di(pyrazin-2-yl)pyridine Ligand[J]. Chinese J. Inorg. Chem., 2017,33(11):2045-2050. doi: 10.11862/CJIC.2017.246
12. [12]
  Nishijo J, Uchida M, Enomoto M, Akita M. A Chromium Bis -acetylide Complex Containing a trans -Diethyl -Ethylenedithio -Substituted Tetrathiafulvalene (TTF) Derivative: Synthesis, Crystal Structures, and Magnetic Properties. Transition Met[J]. Chem., 2021,46(5):373-380.
13. [13]
  Yoshimura A, Misaki Y. Periphery Modification of Tetrathiafulva-lenes: Recent Development and Applications[J]. Chem. Rec., 2021,21:1-13. doi: 10.1002/tcr.202180101
14. [14]
  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 Crys-tal Structure Diversity, and Physical Properties of Tetrathiafulvalene Derivatives Substituted with Various Aryl Groups through Sulfur Bridges. Chem[J]. Eur. J., 2013,19(37):12517-12525. doi: 10.1002/chem.201301819
15. [15]
  Lu X F, Sun J B, Liu Y, Shao J F, Ma L F, Zhang S X, Zhao J, Shao Y L, Zhang H L, Wang Z H, Shao X F. Decorating Tetrathiafulvalene (TTF) with Fluorinated Phenyls through Sulfur Bridges: Facile Syn-thesis, Properties, and Aggregation through Fluorine Interactions[J]. Chem. Eur. J., 2014,20(31):9650-9656.
16. [16]
  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, Struc-ture Diversity and Magnetic Properties[J]. Beilstein J. Org. Chem., 2015,11:850-859. doi: 10.3762/bjoc.11.95
17. [17]
  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.
18. [18]
  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. doi: 10.1039/c3ra41349g
19. [19]
  QI H, LU X F, ZHANG S X, SHAO X F. Arylthio-Substituted/Fused Tetrathiafulvalenes[J]. Chemistry, 2016,79(9):787-792.
20. [20]
  Zou R Q, Sakurai H, Han S, Zhong R Q, Xu Q. Probing the Lewis Acid Sites and CO Catalytic Oxidation Activity of the Porous Metal-Organic Polymer[J]. J. Am. Chem. Soc., 2007,129(27):8402-8403. doi: 10.1021/ja071662s
21. [21]
  Wang Y, Cui S X, Li B, Zhang J P, Zhang Y.. Synthesis and Charac-terization of Monosubstituted TTF and Its Solvent Dependent Mono-and Dication Charge -Transfer Salts[J]. Cryst. Growth Des., 2009,9(9):3855-3858. doi: 10.1021/cg900635f
22. [22]
  Kanehama R, Umemiya M, Iwahori F, Miyasaka H, Sugiura K I, Yamashita M, Yokochi Y, Ito H, Kuroda S I, Kishida H, Okamoto H. Novel ET-Coordinated Copper Complexes: Syntheses, Structures, and Physical Properties (ET=BEDT-TTF=Bis(ethylenedithio)tetrathi-afulvalene)[J]. Inorg. Chem., 2003,42(22):7173-7181.
23. [23]
  Ichikawa S, Kimura S, Takahashi K, Mori H, Yoshida G, Manabe Y, Matsuda M, Tajima H, Yamaura J I.. Intrinsic Carrier Doping in Anti-ferromagnetically Interacted Supramolecular Copper Complexes with (Pyrazino)tetrathiafulvalene (Pyra-TTF) as the Ligand, [CuⅡCl₂(pyra-TTF)] and (Pyra -TTF)₂[Cu₃^ⅠCl₄(pyra -TTF)][J]. Inorg. Chem., 2008,47(10):4140-4145.
24. [24]
  Day P, Kurmoo M, Mallah T, Marsden I R, Friend R H, Pratt F L, Hayes W, Chasseau D, Gaultier J, Bravic G, Ducasse L.. Structure and Properties of Tris[bis(ethylenedithio)tetrathiafulvalenium]tetra-chlorocopper Hydrate, (BEDT -TTF)₃CuCl₄·H₂O: First Evidence for Coexistence of Localized and Conduction Electrons in a Metallic Charge -Transfer Salt[J]. J. Am. Chem. Soc., 1992,114(27):10722-10729.
25. [25]
  Marsden I R, Allan M L, Friend R H, Kurmoo M, Kanazawa D, Day P, Bravic G, Chasseau D, Ducasse L, Hayes W. Crystal and Electron-ic Structures and Electrical, Magnetic, and Optical Properties of Two Copper Tetrahalide Salts of Bis(ethylenedithio) -Tetrathiafulvalene[J]. Phys. Rev. B, 1994,50(4):2118-2127.
26. [26]
  Ichikawa S, Takahashi K, Matsuda M, Tajima H, Mori H. Metallic Coordination Supramolecule, [Cu Cl_0.2Br_1.3(pyra-TTF)^0.5+][J]. J. Mater. Chem., 2010,20(45):10130-10134.
27. [27]
  Armarego W L F, Chai C L L. Purification of Laboratory Chemicals. 5th ed. Amsterdam, Boston: Butterworth-Heinemann, 2003.
28. [28]
  Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K, Puschmann H. OLEX2:A Complete Structure Solution, Refinement and Analysis Program[J]. J. Appl. Crystallogr., 2009,42(2):339-341.
29. [29]
  Sheldrick G M. SHELXL-97, A Program for Crystal Structure Refinement. University of Göttingen, Germany, 1997.
30. [30]
  Zhang S X, Lu X F, Sun J B, Zhao Y L, Shao X F.. Honeycomb Supra-molecular Frameworks of Organic -Inorganic Hybrid Cluster Com-posed of Cation Radical and Keggin-Type Polyoxometalate.[J]. CrystEngComm, 2015,17(22):4110-4116.
31. [31]
  Ishiguro T, Yamaji K, Saito G. Organic Superconductors. 2nd ed. Berlin: Springer, 1998.
32. [32]
  Guionneau P, Kepert C J, Bravic G, Chasseau D, Truter M R, Kurmoo M, Day P. Determining the Charge Distribution in BEDT-TTF Salts[J]. Synth. Met., 1997,86(1):1973-1974.
33. [33]
  Beck J, de Oliveira A B. On the Oxidation of Octamethylenetetrathia-fulvalene by CuBr₂ -Synthesis, Crystal Structure and Magnetic Prop-erties of (OMTTF)₂[J]. Z. Anorg. Allg. Chem., 2009,635(3):445-449.
34. [34]
  Kubo K, Yamashita M. New BEDT -TTF Radical Cation Salt with Mixed Anions: α'-[BEDT-TTF]₂[CuBr₂]_0.4[CuCl₂]_0.6[J]. Crystals, 2012,2(2):284-293.
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