Synthesis, Structure and Electrochemistry of Tetrathiafulvalene Vinylogues Bearing Thienyl and Pyridyl Groups†

doi:10.7503/cjcu20180145

Abstract

Abstract:

Through triethylphosphite-mediated cross-coupling reaction, 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-thione(1) reacted with 2-thiophenecarboxaldehyde(2a) or 3-thiophenecarboxaldehyde(2b) to give 2,2'-[(2-(thiophen-2-ylmethylene)-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]dipyridine(3a) and 2,2'-[(2-(thiophen-3-ylmethylene)-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]dipyridine(3b) with the yields of 64% and 59%, respectively. The dithiafulvalene compounds possessing thienyl and pyridyl groups 3a and 3b were subjected to an iodine-induced oxidative dimerization reactions and then a brief reductive aqueous workup with Na₂S₂O₃ to gain tetrathiafulvalene vinylogues 1,2-bis(4,5-bis(pyridin-2-ylthio)-1,3-dithiol-2-ylidene)-1,2-di(thiophen-2-yl)ethane(4a) and 1,2-bis(4,5-bis(pyridin-2-ylthio)-1,3-dithiol-2-ylidene)-1,2-di(thiophen-3-yl)ethane(4b) with the yields of 24% and 22%, respectively. All novel compounds were identified by the nuclear magnetic resonance spectroscopy(NMR), fourier transform infrared spectroscopy(FTIR) and mass spectroscopy(MS) methods. Meanwhile, the structures of compounds 3a, 3b, 4a and 4b were characterized by X-ray diffraction analysis. The cyclic voltammograms showed that the tetrathiafulvalene vinylogues 4a and 4b displayed quasi-reversible one two-electron redox processes. Combined with quantum chemical calculations, effects of the different thienyl and pyridyl groups substituted tetrathiafulvalene vinylogues 4a and 4b on electrochemical potentials were analysised.

Key words: Tetrathiafulvalene vinylogue, Thiophene, Pyridine, Cyclic voltammetry, Quantum chemical calculation

TrendMD:

ZHAO Bangtun, TAO Jingjing, CHEN Xiaoji, FU Huimin, ZHU Weimin. Synthesis, Structure and Electrochemistry of Tetrathiafulvalene Vinylogues Bearing Thienyl and Pyridyl Groups^†[J]. Chem. J. Chinese Universities, 2018, 39(7): 1449.

Figures/Tables 6

Scheme 1 Synthetic routes of TTFV compounds 4a and 4b

Fig.1 Molecular structures of compounds 3a(A) and 3b(B)

Fig.2 Molecular structures of compounds 4a(A) and 4b(B)

Table 1 Electrochemical data obtained by CV method for compounds 4a and 4b

Compd.	/V	E_pc/V	E_1/2/V
4a	0.513	0.471	0.492
4b	0.600	0.563	0.582

Table 2 Molecular orbitals and ionization energies for compounds 4a and 4b

Compd.	HOMO/eV	LUMO/eV	E_g/eV	IE(Ⅰ)/eV	IE(Ⅱ)/eV
4a	-4.71	-1.04	3.67	5.89	14.72
4b	-4.97	-1.23	3.74	6.15	15.23

Fig.3 Molecular orbitals of the HOMO and LUMO for compounds 4a(A) and 4b(B)

References 19

[1]	Segura J. L., Martín N., Angew. Chem. Int.Ed., 2001, 40, 1372—1409
[2]	Canevet D., Sallé M., Zhang G.X., Zhu D . B.,Chem. Commun., 2009, (17), 2245—2269
[3]	Nielsen M. B., Lomholt C., Becher J., Chem. Soc. Rev., 2000, 29, 153—164
[4]	Zhao B. T., Chen X. H., Ma S. X., Zhu W. M., Chem. Res. Chinese Universities, 2015, 31(6), 930—935
[5]	Yamada J., Sugimoto T., TTF Chemistry Fundamentals and Applications of Tetrathiafulvalene, Springer-Verlag, Berlin,2004, 36, 98
[6]	Feng M., Gao L., Deng Z. T., Ji W., Guo X. F., Du S. X., Shi D. X., Zhang D. Q., Zhu D. B., Gao H. J., J. Am. Chem. Soc., 2007, 129, 2204—2205
[7]	Wen Z., Kan Y. H., Yan W. Y., Ding Y. Y., Wang. X. L., Chem. J. Chinese Universities, 2013, 34(6), 1483—1489
	(温智, 阚玉和, 闫文艳, 丁艳艳, 王新龙.高等学校化学学报,2013, 34(6), 1483—1489)
[8]	Li Q., Geng Y., Duan Y. A., Wang G. Y., Su Z. M., Chem. J. Chinese Universities, 2014, 35(7), 1471—1479
	(李倩, 耿允, 段雨爱, 王光宇, 苏忠民.高等学校化学学报,2014, 35(7), 1471—1479)
[9]	Yoshida Z. I., Kawase T., Awaji H., Sugimoto I., Sugimoto S., Yoneda S., Tetrahedron Lett., 1983, 24, 3469—3472
[10]	Zhao Y. M., Chen G., Mulla K., Mahmud I., Liang S., Dongare P., Thompson D. W., Dawe L. N., Bouzan S., Pure Appl. Chem., 2012, 84, 1005—1025
[11]	Liang S., Chen G., Peddle J., Zhao Y. M., Chem. Commun., 2012, 48, 3100—3102
[12]	Massue J., Bellec N., Guerro M., Bergamini J. F., Hapiot P., Lorcy D., J. Org. Chem., 2007, 72, 4655—4662
[13]	Liang S., Zhao Y. M., Adronov A., J. Am. Chem. Soc., 2014, 136, 970—977
[14]	Yamashita Y., Tomura M., J. Solid State Chem., 2002, 168, 427—432
[15]	Osada M., Kumagai T., Sugimoto M., Nishida J., Yamashita Y., Synthetic Met., 2005, 152, 429—432
[16]	Gontier E., Bellec N., Brignou P., Gohier A., Guerro M., Roisnel T., Lorcy D., Org. Lett., 2010, 12, 2386—2389
[17]	Zhao B. T., Ma S. X., Tao J. J., Zhu W. M., Chem. J. Chinese Universities, 2017, 38(2), 193—199
	(赵邦屯, 马书修, 陶晶晶, 朱卫民.高等学校化学学报,2017, 38(2), 193—199)
[18]	Benahmed-Gasmi A., Frère P., Roncali J., Elandaloussi E., Orduna J., Garin J., Jubault M., Gorgues A., Tetrahedron Lett., 1995, 36, 2983—2986
[19]	Yu Z. X., Cheong P. H., Liu P., Legault C. Y., Wender P. A., Houk K. N., J. Am. Chem. Soc., 2008, 130, 2378—2379

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