Synthesis and Electrochemical, Electro-Optical Properties and Electrochromic Behavior of Properties of Two New Dithienylpyrroles Derivatives and Their Polymer Films

Hua Xue Fa Zhan Qian Yan
Scientific Journal of Frontier Chemical Development
1,2 1,2,3 1,2 1,2

1. 400715
2. 400715
3. 400715
(2,5-(2-)-1H--1--1-(SNS-1AQ) 2,5-(2-)-1H--1--2-
(SNS-2AQ)) 1H NMR, 13C NMR, FT-IR, MS
SEM
Synthesis and Electrochemical, Electro-optical Properties and

Electrochromic Behavior of Properties of Two New Dithienylpyrroles
Derivatives and Their Polymer Films
Liu Wu 1,2*, Xiangkai Fu 1,2,3, Gang Wang1,2, Jun Deng1,2
1. Research Institute of Applied Chemistry, College of Chemistry and Chemical Engineering,
Southwest University, Chongqing, China, 400715
2. The Key Laboratory of Applied Chemistry of Chongqing Municipality, Chongqing, China, 400715
3The Key Laboratory of Eco-environments in Three Gorges Reservoir Region, Ministry of Education,
Chongqing, China, 400715
Email: wuliu19851110@163.com
Abstract: Two new kinds of dithienylpyrroles derivatives (1-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)-anthraquinone (SNS-1AQ) and
2-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)-anthraquinone (SNS-2AQ)) have been prepared. The corresponding polymer films were
successfully synthesized via electropolymerization. The structures of these compounds were characterized and ensured by 1H NMR, 13C
NMR, MS and FT-IR. The corresponding polymer films were successfully synthesized via electropolymerization in three-electrode system.
Their spectroelectrochemical properties, electrochromic behavior, thermal stability, surface morphology, and fluorescence were
investigated by cyclic voltammetry, UV-VIS absorption, thermogravimetric analysis, scanning electron microscopy and fluorescence
emission spectra. The results show that these polymer films have excellent spectroelectrochemical and electrochromic properties.
Key words: Dithienylpyrroles; Polythienylpyrroles; Aminoanthraquinone; Electropolymerization Synthesis and Characterization;
Electrochromic Materials
[1-2]Platt
[3]1965 J. F. Dreger
1969 S. K. Deb
(No.09C26215112399)
( 2009(143 ))
SJFCD Jun. 2012 Vol.2 No.2 PP.27-36 www.sjfcd.org 2011 American V-King Scientific Publishing, LTD | 27
WO3
80
[4-9]
3V
1987Ferraris and Skiles[10]SNS)

(PSNS)[11-33]
2000Enric Brillas25
PtChane-ChingL.ToppareA. Cihaner
1
1.1
1-2-90%Alfa Aesar
AR
PK-6000
KBr
400~4000cm-1AV-300
D/MAX-3C
XRD-NETZSCHSTA-449C ~1000 , 10.0 K/min
KYKY-EM3200 UV-4802H CHI-650B (
)
1.2
1.2.1
22.0 mL 11.8 g N,N- 60 C

24 h 10 mL 93%
[34] 2,5-(2-)-1,4-
1.2.2
2,5-(2-)-1,4-
16 g 15 mL 9.6 mL 5.5 mL
20 C 18 h 10 mL 2 h
3
(: =1: 1)
10 g 80%M.P. 126-127 C1H NMR (300 M, CDCl3): H 7.31-7.35 (t, 2H), 7.23 (s,
2H), 7.04-7.07 (t, 2H), 6.55 (s, 2H) [35]
1.2.3
2,5-(2-)-1H--1--1-
0.25 g 2,5-(2-)-1,4-0.23 g 1-0.02 g 100 mL
28 | SJFCD Jun. 2012 Vol.2 No.2 PP.27-36 www.sjfcd.org 2011 American V-King Scientific Publishing, LTD
3
()(: =2: 1) 0.21 g
48%M.P. 223-224 C. 1H NMR (300 M, CDCl3): H 8.52 (d, J1=7.6 Hz, 1H), 8.23 (d, J2=6.3 Hz, 1H), 8.07-8.09 (t,
J1=7.4 Hz, J2=5.9 Hz, 1H), 7.81-7.86 (t, 1H), 7.70-7.74 (q, 3H), 6.95 (d, J = 4.8 Hz, 2H), 6.71-6.75(t, 4H), 6.59 (d, J =2.7
Hz, 2H). 13C NMR (75 MHz, CDCl3): C 182.6, 181.1, 138.3, 137.9, 135.1, 134.5, 134.4, 134.1, 133.9, 133.8, 132.4,
131.4, 129.1, 128.9, 127.5, 126.8, 126.7, 124.7 124.3, 110.6. FT-IR (KBr, cm-1): 3107, 3085, 3070, 1670, 1580, 1411, 1315,
1279, 1162, 1111, 966, 773, 708, 687. APCI-MS (m/z): Calcd 437; found 437
1.2.4
2,5-(2-)-1H--1--2-
0.25 g 2,5-(2-)-1,4-0.23 g 2-0.02 g 100 mL
3
()(: =2: 1) 0.28 g
65%M.P. 219-220 C. 1H NMR (300 M, CDCl 3): H 8.28-8.34 (t, 3H), 8.20 (s, 1H), 7.80-7.83 (t, 2H), 7.64 (d, J=8.1
Hz, 1H), 7.08 (d, J= 4.8 Hz, 2H), 6.80-6.82 (t, 2H), 6.56-6.59 (t, 2H). 13C NMR (75 MHz, CDCl3): C 182.4, 182.1, 143.8,
135.1, 134.4, 134.3, 134.1, 134.0, 133.5, 133.4, 133.0, 129.8, 128.4, 128.3, 127.4, 127.1, 125.6, 125.0, 111.2. FT-IR (KBr,
cm-1): 3103, 3074, 1671, 1593, 1491, 1405, 1331, 1289, 1160, 1111, 961, 766, 709, 677. APCI-MS (m/z): Calcd 437; found
437. 1
1 2,5-(2-)-1H--1--1/2-
2
2.1
2 (0.02 cm2) 2,5-(2-)-1H--1--1/2-(P1
P2) 1 2 0.95 V
0.94 V
0.50 V/0.70 V 0.53 V/0.70 V 1 2
(0.02 cm2)
2 0.01 M Ag/AgCl 100 mV/s 2,5-(2-)-1H-

-1--1/2-(1/2)
2.2
3 4 P1 P2
1 2
3 0.01 M 2,5-(2-)-1H--1--1-(P1)
4 0.01 M 2,5-(2-)-1H--1--2-(P2)

2.3
5 (a)(b) ITO P1 P2
1 2 256 nm322 nm 255 nm

327 nm255 nm 256 nm 322 nm 327 nm
3.4(Eg = 1241/onset) P1 P2
EgP1 P2 2.20 eV 2.13 eV 2.61 eV
Eg Eg
5 2,5-(2-)-1H--1--1/2-(a(P1)b(P2))()
6 P1 P2 -1.2 V 1.2 V
P1--* 411 nm
520 nm, 650 nm and 900 nm P2--* 414
nm 780 nm890 nm
6 Pt Ag/AgCl 0.01 M 2,5-(2-)-1H--1--1/2-

ITO (P1/P2)(a) -1.2 V; (b) -1.0 V; (c) -0.8 V; (d) -0.6 V; (e) -0.4 V; (f)
-0.2 V; (g) 0 V; (h) 0.2 V; (i) 0.4 V; (j) 0.6 V; (k) 0.8 V; (l) 1.0 V; (m) 1.2 V. 2,5-(2-)-1H--1--1/2-+1.0
V, +0.7 V, 0 V, -0.5 V, -1.0 V
2.4
7 8 -1.2 V 1.2 V 10 s 780 nm
P1 P2 P1 P2
95% P1 4 s 4.5 s P2 3.5 s 3
s
7 (a) 2,5-(2-)-1H--1--1-(P1) 0.01 M 780 nm

(b)
8 (a) 2,5-(2-)-1H--1--2-(P2) 0.01 M 780 nm

(b)
7 8 P1 P2 780 nm ( OD)
(CE)
OD=log Tcolored / Tbleached and CE= OD/Qd
Tcolored Tbleached Qd /
P1 0.15 105 cm2/CP2 0.13 98 cm2/C
2.5
9 P1 P2 P1 P2
300 C 200 C 200 C300 C
300 C P2 P1 P2
P1
9 2,5-(2-)-1H--1--1/2-(P1 P2) N2 10 C/min

1000 C
2.6
10(a)(b) P1 P2 P1 P2
1 2 12 P1P2
1
10 (a)
2,5-(2-)-1H--1--1-(P1)(b) 2,5-(2-)-1H--1--2-(P2)
1
(V)
(nm)
(V)
(eV)
(V)
(nm)
0.6
0.6
430
2.61
0.94
345
0.95
256,332
P1
0.95
0.7
414
2.20
0.94
255,327
P2
0.79
0.58
411
2.13
2.7
0.2 mmol/L (0.01 mol/L)
ITO ITO
ClO4-
12 11 P2 12
P2 1.5 V
4 s 3.5 s
(+1.5 V)
(-1.5 V)
11. 2,5-(2-)-1H--1--2-(P2) 1.5 V
12.
(P1 P2)
P1 P2
-1.5 V 1.5V
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1985-
2005.09-2009.07 2009.09-
Emailwuliu19851110@163.com
1945-
Emailfxk@swu.edu.cn

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Scientific Journal of Frontier Chemical Development

1,2 1,2,3 1,2 1,2