Citation: Qi ZUO, Long-Fei MA. Synthesis and crystal structure of the charge transfer complexes of arylthiotetrathiafulvalenes and iodine[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(10): 1869-1876. doi: 10.11862/CJIC.2023.156 shu

Synthesis and crystal structure of the charge transfer complexes of arylthiotetrathiafulvalenes and iodine

Qi ZUO ,
Long-Fei MA ^,

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

Corresponding author: Long-Fei MA, malongfei@hnp.edu.cn
Received Date: 2 May 2023
Revised Date: 13 June 2023

Figures(5)

Three charge-transfer (CT) complexes (1^+·)(I₃)·I₂, (2^+·)(I₅)·I₂, and (3²⁺)(I₃)₂ have been prepared via solvent evaporation method comprising arylthio - substituted tetrathiafulvalene derivatives (Ar-S-TTF) and iodine. Single crystal X-ray diffraction, UV-Vis spectrum, and cyclic voltammetry were used to characterize the complexes. Complex (1^+·)(I₃)·I₂ crystallizes in the C2/c space group. 1^+· takes the chair configuration. The asymmetric unit contains half of 1^+· ions, half of I₃^- ions, and half of I₂ molecules. The charge transfer between compound 1 with iodine is consistent in the complex in solution. Complex (2^+·)(I₅)·I₂ crystallizes in the P1 space group, and 2^+· takes the chair conformation. The asymmetric unit contains one 2^+· ion, one I₅^- ion, and one I₂ molecule. Complex (3²⁺)(I₃)₂ crystallizes in the Pbca space group, and 3²⁺ takes the unique planar configuration. The asymmetric unit contains one 3²⁺ ion and two I₃^- ions. Compounds 2 and 3 exhibit different charge transfers with iodine in solution and the complex. The iodine components in the complexes show various structures including the 1D chain of I₃^- or I₅^-/I₂, and 2D iodine networks comprised of I₂ and I₃^-.
- tetrathiafulvalene,
- iodine,
- crystal structure,
- charge transfer complexes
1. [1]
  Williams J M, Ferraro J R, Thorn R J, Carlson K D, Geiser U, Wang H H, Kini A M, Whangbo M H. Organic superconductors (including fullerenes). Englewood Cliffs, NJ: Printice Hall, 1992.
2. [2]
  Ishiguro T, Yamaji K, Saito G. Organic superconductors. 2nd ed. Berlin: Springer, 1998.
3. [3]
  Fourmigué M, Batail P. Activation of hydrogen- and halogen-bonding interactions in tetrathiafulvalene-based crystalline molecular conductors[J]. Chem. Rev., 2004,104(11):5379-5418. doi: 10.1021/cr030645s
4. [4]
  Mori H. Materials viewpoint of organic superconductors[J]. J. Phys. Soc. Jpn., 2006,75(5)051003. doi: 10.1143/JPSJ.75.051003
5. [5]
  Wang H Y, Su J, Ma J P, Yu F, Leong C F, D'Alessandro D M, Kurmoo M, Zuo J L. Concomitant use of tetrathiafulvalene and 7,7,8,8-tetracyanoquinodimethane within the skeletons of metal-organic frameworks: Structures, magnetism, and electrochemistry[J]. Inorg. Chem., 2019,58(13):8657-8664. doi: 10.1021/acs.inorgchem.9b01000
6. [6]
  Blake J A, Li W S, Lippolis V, Schröder M A, Devillanova F O, Gould R, Parsons S, Radek C. Template self-assembly of polyiodide networks[J]. Chem. Soc. Rev., 1998,27(3):195-206. doi: 10.1039/a827195z
7. [7]
  Zeng M H, Wang Q X, Tan Y X, Hu S, Zhao H X, Long L S, Kurmoo M. Rigid pillars and double walls in a porous metal-organic framework: Single-crystal to single-crystal, controlled uptake and release of iodine and electrical conductivity[J]. J. Am. Chem. Soc., 2010,132(8):2561-2563. doi: 10.1021/ja908293n
8. [8]
  Yu F, Li D D, Cheng L, Yin Z, Zeng M H, Kurmoo M. Porous supramolecular networks constructed of one-dimensional metal-organic chains: Carbon dioxide and iodine capture[J]. Inorg. Chem., 2015,54(4):1655-1660. doi: 10.1021/ic502650z
9. [9]
  Zeng M H, Yin Z, Tan Y X, Zhang W X, He Y P, Kurmoo M. Nanoporous cobalt(Ⅱ) MOF exhibiting four magnetic ground states and changes in gas sorption upon post-synthetic modification[J]. J. Am. Chem. Soc., 2014,136(12):4680-4688. doi: 10.1021/ja500191r
10. [10]
  Tomase P, Marcin Ś, Rafał K. Molecular self-assembly of 1D infinite polyiodide helices in a phenanthrolinium salt[J]. Dalton Trans., 2021,50(8):2800-2806. doi: 10.1039/D0DT04042H
11. [11]
  Ma L F, Peng H L, Lu X F, Liu L, Shao X F. A weaker donor shows higher oxidation state upon aggregation[J]. RSC Adv., 2018,8(31):17321-17324. doi: 10.1039/C8RA02956C
12. [12]
  Lin J X, Martí-Rujas J, Metrangolo P, Pilati T, Radice S, Resnati G, Terraneo G. Solution and solid state synthesis of the discrete polyiodide I₇^3- under modular cation templation[J]. Cryst. Growth Des., 2012,12(11):5757-5762. doi: 10.1021/cg301262k
13. [13]
  Yin Z, Wang Q X, Zeng M H. Iodine release and recovery, influence of polyiodide anions on electrical conductivity and nonlinear optical activity in an interdigitated and interpenetrated bipillared-bilayer metal-organic framework[J]. J. Am. Chem. Soc., 2012,134(10):4857-4863. doi: 10.1021/ja211381e
14. [14]
  Madhu S, Evans H A, Vicky V T, Doan-Nguyen , John G L, Wu G, Michael L, Seshadri R, Wudl F. Infinite polyiodide chains in the pyrroloperylene-iodine complex: Insights into the starch-iodine and perylene-iodine complexes[J]. Angew. Chem. Int. Ed., 2016,55(28):8032-8035. doi: 10.1002/anie.201601585
15. [15]
  Küpper F C, Feiters M C, Olofsson B, Kaiho T, Yanagida S, Zimmermann M B, Carpenter L J, Luther G W, Lu Z L, Jonsson M, Kloo L. Commemorating two centuries of iodine research: An interdisciplinary overview of current research[J]. Angew Chem. Int Ed., 2011,50(49):11598-11620. doi: 10.1002/anie.201100028
16. [16]
  Savastano M, Bazzicalupi C, Gellini C, Bianchi A. Genesis of complex polyiodide networks: Insights on the blue box/I^-/I₂ ternary system[J]. Crystals, 2020,10(5)387. doi: 10.3390/cryst10050387
17. [17]
  Yamada J, Sugimoto T. TTF chemistry: Fundamentals and applications of tetrahiafulvalenes. Berlin, Heidelberg, New York: Kodansha Ltd: Tokyo and Springer-Verlag, 2004.
18. [18]
  Wang H Y, Cui L, Xie J Z, Leong C F, D'Alessandro D M, Zuo J L. Functional coordination polymers based on redox-active tetrathiafulvalene and its derivatives[J]. Coord. Chem. Rev., 2017,345(15):342-361.
19. [19]
  Wang H Y, Ge J Y, Hua C, Jiao C Q, Wu Y, Leong C F, D'Alessandro D M, Liu T, Zuo J L. Photo- and electronically switchable spin-crossover iron(Ⅱ) metal-organic frameworks based on a tetrathiafulvalene ligand[J]. Angew. Chem. Int. Ed., 2017,56(20):5465-5470. doi: 10.1002/anie.201611824
20. [20]
  Armarego W L F, Chai C L L. Purification of laboratory chemicals. 5th ed. Amsterdam, Boston: Butterworth-Heinemann, 2003.
21. [21]
  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
22. [22]
  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. doi: 10.1107/S0021889808042726
23. [23]
  Sheldrick G M. SHELXL-97, A program for crystal structure refinement. University of Göttingen, Germany, 1997.
24. [24]
  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. doi: 10.1002/cjoc.201800215
25. [25]
  Zhang S X, Lu X F, Sun J B, Zhao Y L, Shao X F. Honeycomb supramolecular frameworks of organic-inorganic hybrid cluster composed of cation radical and Keggin-type polyoxometalate[J]. CrystEngComm, 2015,17(22):4110-4116. doi: 10.1039/C5CE00510H
26. [26]
  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.
27. [27]
  Kloo L, Rosdahl J, Svensson P H. On the intra - and intermolecular bonding in polyiodides[J]. Eur. J. Inorg. Chem., 2002(5):1203-1209.
28. [28]
  Korobeinikov N A, Usoltsev A N, Shentseva I A, Abramov P A, Korolkov I V, Plusnin P E, Kolesov B A, Sokolov M N, Adonin S A. Triiodide salts of 4-dimethylamino - and 3-bromo-1-methylpyridinum: Crystal structures and features of non-covalent I⋯I interaction in solids[J]. J. Struct. Chem., 2022,63(6):988-995. doi: 10.1134/S0022476622060178
29. [29]
  Savastano M, Bazzicalupi C, Bianchi A. Novel cyclen-polyiodide complexes: A reappraisal of Ⅰ—Ⅰ covalent and secondary bond limits[J]. Dalton Trans., 2022,51(28):10728-10739. doi: 10.1039/D2DT00185C
30. [30]
  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(37):12517-12525. doi: 10.1002/chem.201301819
31. [31]
  Lu X F, Sun J B, Liu Y, Shao J F, Ma L F, Zhang S X, Zhao J L, Shao Y, 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(31):9650-9656. doi: 10.1002/chem.201402327
32. [32]
  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.
33. [33]
  Lu X F, Sun J B, Zhang S X, Ma L F, Liu L, Qi H, Shao Y L, Shao X F. Donor-acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes[J]. Beilstein J. Org. Chem., 2015,11:1043-1051. doi: 10.3762/bjoc.11.117
34. [34]
  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. doi: 10.3762/bjoc.11.95
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