Synthesis, Structures and Electrochemical Properties of Pyridine-based Tetrathiafulvalene Derivatives†

doi:10.7503/cjcu20160625

Abstract

Abstract:

Using the ethyl acetoacetate/Cu₂O system, 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-thione(2a), 4,5-bis(pyridin-3-ylthio)-1,3-dithiole-2-thione(2b) and 4,5-bis(pyridin-4-ylthio)-1,3-dithiole-2-thione(2c) were prepared by the reaction of di(tetraehylammonium)-bis(1,3-dithiol-2-thione-4,5-dithiocate) zincate with 2-iodopyridine(1a), 3-iodopyridine(1b) and 4-iodopyridine(1c) with the yields of 88%, 55% and 60%, respectively. Thiones 2a, 2b and 2c were conversed to 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-one(3a), 4,5-bis(pyridin-3-ylthio)-1,3-dithiole-2-one(3b) and 4,5-bis(pyridin-4-ylthio)-1,3-dithiole-2-one(3c) under the presence of Hg(OAc)₂ in almost quantitative yields. Consequently, the pyridine-tetrathiafulvalene compounds 2,3,6,7-tetrakis(pyridine-2-ylthio) tetrathiafulvalene(4a), 2,3,6,7-tetrakis(pyridine-3-ylthio) tetrathiafulvalene(4b) and 2,3,6,7-tetrakis(pyridine-4-ylthio) tetrathiafulvalene(4c) were obtained correspondingly through triethylphosphite-mediated self-coupling reactions of 3a, 3b and 3c with the yields of 80%, 74% and 69%. All novel compounds were characterized by proton and carbon nuclear magnetic resonance spectroscopy(¹H NMR and ¹³C NMR), fourier transform infrared spectroscopy(FTIR) and mass spectroscopy(MS) methods. Meanwhile, the structures of 4b and 4c was identified by X-ray diffraction analysis. The cyclic voltammograms showed that the pyridine-tetrathiafulvalene 4a, 4b and 4c displayed two-electron quasi-reversible redox processes. Combined with quantum chemical calculations, the effects of the different pyridyl substituted tetrathiafulvalenes 4a, 4b and 4c on electrochemical potentials were analysised.

Key words: Tetrathiafulvalene, Pyridine, Crystal structure, Cyclic voltammetry, Quantum chemical calculation

CLC Number:

O621.25

TrendMD:

ZHAO Bangtun, MA Shuxiu, TAO Jingjing, ZHU Weimin. Synthesis, Structures and Electrochemical Properties of Pyridine-based Tetrathiafulvalene Derivatives^†[J]. Chem. J. Chinese Universities, 2017, 38(2): 193.

Figures/Tables 7

Scheme 1 General synthetic routes for 2,3,6,7-tetrakis(pyridine-2-ylthio)tetrathiafulvalene(4a), 2,3,6,7-tetrakis(pyridine-3-ylthio)tetrathiafulvalene(4b) and 2,3,6,7-tetrakis(pyridine-4-ylthio)tetrathiafulvalene(4c)

Table 1 X-ray diffraction data for pyridine-based tetrathiafulvalenes 4b and 4c

Compound	4b	4c
Empirical formula	C₂₆H₁₆N₄S₈	C₂₆H₁₆N₄S₈
Formula mass	640.91	640.91
Crystal size/mm	0.25×0.20×0.15	0.35×0.35×0.20
Crystal system	Triclinic	Triclinic
Space group	P1	P1
a/nm	0.52575(11)	0.56065(11)
b/nm	1.0461(2)	1.0114(2)
c/nm	1.2788(3)	1.2722(3)
α/(°)	92.58(3)	102.39(3)
β/(°)	92.22(3)	91.25(3)
γ/(°)	98.05(3)	94.25(3)
Volume/nm³	0.6950(2)	0.7021(2)
Z	1	1
Calculated density/(g·cm^-3)	1.531	1.516
Absorption coefficient/mm^-1	0.668	0.661
F(000)	328	328
θ range for data collection/(°)	2.60—25.50	2.34—24.99
Limiting indices	-6≤h≤6,-12≤k≤12,-15≤l≤15	-6≤h≤6,-11≤k≤11,-14≤l≤15
Reflections collected/unique	5819/2442(R_int=0.0471)	5977/2470(R_int=0.0199)
Completeness to θ=25.00°(%)	99.6	99.8
Absorption correction	Semi-empirical from equivalents	Semi-empirical from equivalents
Max. and min. transmission	0.9064 and 0.8508	0.8791 and 0.8015
Refinement method	Full-matrix least-squares on F²	Full-matrix least-squares on F²
Data/restraints/parameters	2442/0/172	2470/0/172
Goodness of fit on F²	1.087	1.084
Final R indices[I>2σ(I)]	R₁=0.0524, wR₂=0.1497	R₁=0.0296, wR₂=0.0790
R index(all data)	R₁=0.0656, wR₂=0.1741	R₁=0.0353, wR₂=0.0841
Largest diff. peak and hole/(e·nm^-3)	0.521 and -0.392	0.206 and -0.234
CCDC number	1472060	1472061

Fig.1 Crystal structures of compounds 4b(A) and 4c(B)

Fig.2 CV diagrams of compound 4a(a), 4b(b) and 4c(c)

Table 2 Electrochemical data(V) of compounds 4a, 4b and 4c measured by cyclic voltammetry

Compound	$E pa 1$	$E pc 1$	$E pa 1$ - $E pc 1$	$E pa 2$	$E pc 2$	$E pa 2$ - $E pc 2$	$E 121$	$E 122$
4a	0.613	0.552	0.061	0.792	0.732	0.060	0.5825	0.762
4b	0.762	0.691	0.071	1.046	0.981	0.065	0.726	1.014
4c	0.855	0.787	0.068	1.127	1.029	0.098	0.821	1.078

Table 2 Electrochemical data(V) of compounds 4a, 4b and 4c measured by cyclic voltammetry

Compound	$E pa 1$	$E pc 1$	$E pa 1$ - $E pc 1$	$E pa 2$	$E pc 2$	$E pa 2$ - $E pc 2$	$E 121$	$E 122$
4a	0.613	0.552	0.061	0.792	0.732	0.060	0.5825	0.762
4b	0.762	0.691	0.071	1.046	0.981	0.065	0.726	1.014
4c	0.855	0.787	0.068	1.127	1.029	0.098	0.821	1.078

Table 3 Molecular orbital energy of compounds 4a, 4b and 4c

Compound	HOMO/eV	LUMO/eV	E_g/eV	IE/eV
4a	-4.64	-1.10	3.54	5.96
4b	-4.71	-1.36	3.35	6.06
4c	-5.12	-1.69	3.42	6.46

Fig.3 Molecular orbital of the HOMO and LUMO for 4a(A), 4b(B) and 4c(C)

References 23

[1]	Yamada J., Sugimoto T., TTF Chemistry Fundamentals and Applications of Tetrathiafulvalene, Springer, Verlag, Berlin,2004, 36, 98
[2]	Nielsen M. B., Lomholt C., Becher J., Chem. Soc. Rev., 2000, 29, 153—164
[3]	Segura J. L., Martín N., Angew. Chem. Int. Ed., 2001, 40, 1372—1409
[4]	Nazario M., Luis S., María Ángeles H., Beatriz I., Dirk M. G., Acc. Chem. Res., 2007, 40, 1015—1024
[5]	Canevet D., Sallé M., Zhang G.X., Zhu D. B.,Chem. Commun., 2009, (17), 2245—2269
[6]	Bergkamp J. J., Decurtins S., Liu S. X., Chem. Soc. Rev., 2015, 44, 863—874
[7]	Zhao B. T., Chen X. H., Ma S. X., Zhu W. M., Chem. Res. Chinese Universities,2015, 31(6), 930—935
[8]	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)
[9]	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)
[10]	Fabrice P., Boris L. G., Olivier M., Olivier C., Lahcéne O., Acc. Chem. Res., 2015, 48, 2834—2842
[11]	Chahma M., Wang X. S., Van des Est A., Pilkington M., J. Org. Chem., 2006, 71, 2750—2755
[12]	Goeb S., Bivaud S., Croué V., Vajpayee V., Allain M., Sallé M., Materials,2014, 7, 611—622
[13]	Zhao Y. P., Wu L. Z., Si G., Liu Y., Xue H., Zhang L. P., Tung C. H., J. Org. Chem., 2007, 72, 3632—3639
[14]	Balandier J.Y., Belyasmine A., Sallé M.,Eur. J. Org. Chem., 2008, (2), 269—276
[15]	Ota A., Ouahab L., Golhen S., Cador O., Yoshida Y., Saito G., New J. Chem., 2005, 29, 1135—1140
[16]	Wang Q., Day P., Griffiths J. P., Nie H., Wallis J. D., New J. Chem., 2006, 30, 1790—1800
[17]	Benhaoua C., Mazari M., Mercier N., Le D. F., Sallé M., New J. Chem., 2008, 32, 913—916
[18]	Jia C., Zhang D., Guo X., Wan S., Xu W., Zhu D.,Synthesis, 2002, (15), 2177—2182
[19]	Sun J. B., Lu X. F., Shao J. F., Cui Z. L., Shao Y., Jiang G. Y., Yu W., Shao X. F., RSC Adv., 2013, 3, 10193—10196
[20]	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., Chem. Eur. J., 2013, 19, 12517—12525
[21]	Sun J. B., Lu X. F., Ishikawa M., Nakano Y., Zhang S. X., Zhao J. L., Shao Y. L., Wang Z. H., Yamochi H., Shao X. F., J. Mater. Chem. C,2014, 2, 8071—8076
[22]	Lu X., Sun J., Zhang S., Ma L., Liu L., Qi H., Shao Y., Shao X., Beilstein J. Org. Chem., 2015, 11, 1043—1051
[23]	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