含吡啶基四硫富瓦烯衍生物的合成、 结构和电化学性质

doi:10.7503/cjcu20160625

摘要/Abstract

摘要：

在乙酰乙酸乙酯和氧化亚铜共同催化下, 二-(1,3-二硫环戊烯-2-硫酮-4,5-二硫)合锌酸四乙基铵盐分别与2-碘吡啶(1a)、 3-碘吡啶(1b)和4-碘吡啶(1c)反应, 制得硫酮化合物2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2a)、 2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2c). 在醋酸汞催化下, 硫酮化合物2a, 2b和2c分别被氧化为2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-酮(3a)、 2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-酮(3b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-酮(3c). 以亚磷酸三乙酯为偶联剂, 氧酮化合物3a, 3b和3c分别发生自偶联反应生成2,3,6,7-四(2-吡啶硫基)四硫富瓦烯(4a)、 2,3,6,7-四(3-吡啶硫基)四硫富瓦烯(4b)和2,3,6,7-四(4-吡啶硫基)四硫富瓦烯(4c). 采用核磁共振波谱(NMR)、傅里叶变换红外光谱(FTIR)和质谱(MS)分析了所合成化合物的结构和组成, 通过X射线衍射分析确认了吡啶基四硫富瓦烯衍生物4b和4c的晶体结构. 循环伏安法研究结果表明, 化合物4a, 4b和4c呈现准可逆的两电子转移过程, 结合量子化学计算, 分析了不同位置取代的吡啶基对四硫富瓦烯电化学电势的影响.

关键词: 四硫富瓦烯, 吡啶, 晶体结构, 循环伏安, 量化计算

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

中图分类号:

O621.25

TrendMD:

赵邦屯, 马书修, 陶晶晶, 朱卫民. 含吡啶基四硫富瓦烯衍生物的合成、结构和电化学性质. 高等学校化学学报, 2017, 38(2): 193.

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

图/表 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)

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