3
.66 ml, 9.14 mmol) was added dropwise to the solution
References
then left to stir for 0.5 h. A second THF solution (10 ml)
of dried zinc chloride was prepared (1.37 g, 10.05 mmol) and
was slowly transferred to the first via cannula. The zinc
chloride containing solution was allowed to stir at 278 uC for
1
2
S. Kirchmeyer and K. Reuter, J. Mater. Chem., 2005, 15, 2077.
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h further and subsequently warmed to ambient temperature.
A third THF solution (15 ml) of 2,5-dibromo-3,4-ethylene-
dithiathiophene 3 (1.52 g, 4.57 mmol) and freshly prepared
tetrakis(triphenylphosphine)palladium(0) catalyst (5 mol%,
0
.53 g, 0.46 mmol) was also transferred via cannula to the
main reaction flask and allowed to stir for 0.5 h at room
temperature before heating to reflux overnight. (After all
cannula transfers are completed, a further 5–10 ml of solvent is
flushed through the needle to ensure complete reagent
transfer.) The reaction was cooled to room temperature and
THF removed. The mixture was redissolved in DCM (75 ml)
and washed with saturated ammonium chloride solution
7
8
1
997, 84, 215.
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0 Y. H. Ha, N. Nikolov, S. K. Pollack, J. Mastrangelo, B. D. Martin
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(
3 6 100 ml) and water (2 6 100 ml) before drying and
removal of solvent. The product was purified by HPLC
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1
2 B. D. Reeves, B. C. Thompson, K. A. Abboud, B. E. Smart and
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eluted with a hexane and ethyl acetate mixture (2 : 1). The
crude product was furnished as an orange solid and
1
3 B. D. Reeves, C. R. G. Grenier, A. A. Argun, A. Cirpan,
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1
recrystallised from DCM to give yellow crystals (9%).
NMR (CDCl ): d
C NMR (CDCl
09.85, 99.97, 65.24, 64.75, 28.96; MS (EI): 454 (100%);
IR: 3102, 2915, 2874, 1495, 1439, 1365, 1277, 1166, 1067, 1021,
H
7
559.
3
H
6.45 (2H, s), 4.33 (8H, m), 3.24 (4H, s);
): d 141.70, 139.04, 126.14, 124.06,
1
1
4 L. Huchet, S. Akoudad and J. Roncali, Adv. Mater., 1998, 10, 541.
5 H. Brisset, A. E. Navarro, C. Moustrou, I. F. Perepichka and
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1
3
3
C
1
16 C. L. Gaupp and J. R. Reynolds, Macromolecules, 2003, 36, 6305.
17 A. Berlin, G. Zotti, S. Zecchin, G. Schiavon, B. Vercelli and
2
1
9
76, 929, 909, 859 cm ; Anal. calcd. for C18
14 4 5
H O S : C,
A. Zanelli, Chem. Mater., 2004, 16, 3667.
4
7.55; H, 3.10; S, 35.27. Found: C, 47.34; H, 3.08; S, 34.06%;
1
1
2
8 Y. Lee, S. Sadki, B. Tsuie, P. Schottland and J. R. Reynolds,
Synth. Met., 2001, 119, 77.
9 G. A. Sotzing, J. R. Reynolds and P. J. Steel, Chem. Mater., 1996,
Mp 193 uC.
8, 882.
2
,5-Bis(3,4-ethylenedithiathiophene)-3,4-ethylenedioxythiophene
0 F. Wang, M. S. Wilson, R. D. Rauh, P. Schottland,
B. C. Thompson and J. R. Reynolds, Macromolecules, 2000, 33,
(
SOS)
2
083.
The same procedure was utilised as for OSO, except 3,4-
ethylenedithiathiophene and 2,5-dibromo-3,4-ethylenedioxy-
thiophene were used. The target compound SOS and
2
2
2
2
1 J. Cao, J. W. Kampf and M. D. Curtis, Chem. Mater., 2003, 15,
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4
1
bis(EDTT)
as a side product were isolated by flash
chromatography on a silica column eluted with petrol and
DCM (4 : 1) as yellow and green solids respectively and
purified by recrystallisation from DCM. Solution 1: EDTT
(
2.11 g, 12.01 mmol), n-BuLi (2.5 M, 5.61 ml, 12.01 mmol)
and THF (30 ml). Solution 2: zinc chloride (1.65 g,
2.10 mmol) and THF (10 ml). Solution 3: DBEDOT 4
1.81 g, 6.05 mmol), Pd(PPh (5 mol%, 0.210 g, 0.182 mmol)
25 H. J. Spencer, R. Berridge, D. J. Crouch, S. P. Wright, M. Giles,
I. McCulloch, S. J. Coles, M. B. Hursthouse and P. J. Skabara,
J. Mater. Chem., 2003, 13, 2075.
1
(
3 4
)
2
6 A. Bondi, J. Phys. Chem., 1964, 68, 441.
and THF (20 ml).
1
SOS: Yield (7%); H NMR (CDCl ): d 7.04 (2H, s), 4.42
27 T. Khan, J. J. W. McDouall, E. J. L. McInnes, P. J. Skabara,
P. Fr e` re, S. J. Coles and M. B. Hursthouse, J. Mater. Chem., 2003,
13, 2490.
3
H
1
3
(
4H, s), 3.30 (8H, m); C NMR (CDCl ): dC 138.45, 126.13,
3
2
8 D. J. Crouch, P. J. Skabara, J. E. Lohr, J. J. W. McDouall,
M. Heeney, I. McCulloch, D. Sparrowe, M. Shkunov, S. J. Coles,
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1
18.18, 109.93, 65.06, 29.11, 27.97; MS (CI): 487 (11%), 217
(
98%), 189 (100%), 84 (51%); IR: 1502, 1450, 1442, 1407, 1361,
2
1
29 P. J. Skabara, R. Berridge, K. Prescott, L. M. Goldenberg, E. Ort ´ı ,
R. Viruela, R. Pou-Am e´ rigo, A. S. Batsanov, J. A. K. Howard,
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30 P. T. Henderson and D. M. Collard, Chem. Mater., 1995, 7, 1879.
31 Charge Percolation in Electroactive Polymers, in Electroactive
Polymer Chemistry, Part 1 Fundamentals, ed. M. E. G. Lyons,
Plenum Press, New York, 1994.
1
312, 1282, 1084, 855 cm ; Anal. calcd. for C H O S : C,
18 14 2 7
4
4.41; H, 2.90; S, 46.11. Found: C, 44.01; H, 2.58; S, 45.12%;
Mp 245 uC.
Bis(EDTT): Yield (8%); H NMR (CDCl ): d 7.11 (2H, s),
1
3
H
1
.27 (8H, s); C NMR (CDCl
3
3
3 C
): d 126.60, 126.31, 125.38,
1
19.60, 28.44, 27.74; MS (CI): 347 (100%), 290 (20%), 246
32 N. Sakmeche, J. J. Aaron, M. Fall, S. Aeiyach, M. Jouni,
J. C. Lacroix and P. C. Lacaze, Chem. Commun., 1996, 2723.
33 B. Sankaran and J. R. Reynolds, Macromolecules, 1997, 30, 2582.
(
17%), 201 (16%), 93 (19%), 69 (20%); IR: 1455, 1405, 1279,
2
1
1
10 6
262, 1041, 935, 853 cm ; Anal. calcd. for C12H S : C, 41.57;
3
3
4 H. Huang and P. G. Pickup, Chem. Mater., 1998, 10, 2212.
5 Y. Fu, H. Cheng and R. L. Elsenbaumer, Chem. Mater., 1997, 9,
1720.
H, 2.91; S, 55.51. Found: C, 41.67; H, 3.27; S, 54.79%; Mp
4
1
1
74–176 uC (lit. 178 uC).
This journal is ß The Royal Society of Chemistry 2005
J. Mater. Chem., 2005, 15, 4783–4792 | 4791