p-Conjugated Multiple Donor–Acceptor Motifs
FULL PAPERS
Several drops of pyridine were added, and the mixture was refluxed
under Ar for 1 h. Then, the clear brown solution was cooled down to
about 1008C; EtOH (0.5 mL) was carefully added dropwise to quench
the residual thionyl chloride. The color of the solution immediately
changed to yellow, and a significant amount of precipitate was formed.
This hot mixture was filtered quickly, and the precipitate was washed
with hot toluene. The filtrate was concentrated under vacuum to a small
volume, and EtOH (20 mL) was added to precipitate 3 as a yellow
powder. Yield: 125 mg (52%); m.p. 176–1788C; IR (KBr): n˜ =3435, 1484,
vacuum. The residue was redissolved in CH2Cl2 while the insoluble part
was filtered off. The filtrate was concentrated to afford 2 as a brown
solid. Yield: 110 mg (77%); m.p.>2308C (dec.); IR (KBr): n˜ =3433,
2923, 2852, 1608, 1503, 1465, 1214, 1164, 817 cmꢀ1; 1H NMR (300 MHz,
CDCl3): d=7.05 (d, J=8.7 Hz, 8H), 6.77 (d, J=8.4 Hz, 8H), 2.53(t,
J=7.5 Hz, 8H), 1.54 (m, 8H), 1.28 (m, 16H), 0.88 ppm (t, J=6.6 Hz,
12H); 13C NMR (75 MHz, CDCl3): d=153.9, 137.3, 129.6, 115.1, 114.8,
35.1, 31.5, 31.2, 22.5, 14.0 ppm; MS (MALDI-TOF): m/z calcd for
C58H68N4O4S4: 1012.41; found: 1012.66; elemental analysis calcd (%) for
C58H68N4O4S4: C 68.74, H 6.76, N 5.53; found: C 68.35, H 6.89, N 5.22.
1240, 1070, 860 cmꢀ1 1H NMR (300 MHz, [D6]DMSO): d=8.68 ppm (s,
;
2H); 13C NMR (75 MHz, [D6]DMSO): d=214.9, 152.5, 143.4, 114.0 ppm;
MS (EI): m/z (%): 242 (95) [M+]; elemental analysis calcd (%) for
C7H2N2S4: C 34.69, H 0.83, N 11.56; found: C 34.91, H 0.83, N 11.14.
2,5,8,11,13,23-Hexakis(1,1-dimethylethyl)-18-[2,5,8,11,13,23-hexakis(1,1-
dimethylethyl)-16,20-bis(4-pentylphenoxy)
g]tetrabenz[7,8:9,10:11,12:13,14]ovaleno [3,4-b]quinoxalin-18-ylidene]-
16,20-bis(4-pentylphenoxy)[1,3]dithiolo[4,5-g]tetrabenz
[7,8:9,10:11,12:13,14]ovaleno
[3,4-b] quinoxaline[24] (1)
ACHUTGTNRENN[GU 1,3]dithioloACHTUNGTERN[NUGN 4,5-
A
ACHTUNGTRENNUNG
4,8-DibromoACHTUNGTRENNUNG[1,3]dithioloACHTUTGNREN[NUGN 4,5-f]-2,1,3-benzothiadiazol-6-one (4)
AHCTUNGTRENNUNG
The solution of Br2 (1.2 mL, 23 mmol) in 47% aqueous HBr solution
(10 mL) was slowly added to the suspension of 3 (1.5 g, 6.2 mmol) in
47% aqueous HBr solution (20 mL). The resulting solution was refluxed
for 8 h (TLC monitoring). If bromination is incomplete, more Br2
(1.2 mL) should be added to this suspension. Upon completion of the re-
action, the resulting solid was filtered off and washed three times with
H2O to afford 4. Yield: 1.62 g (68%); m.p. 236–2378C; IR (KBr): n˜ =
A solution of 2 (15 mg, 0.015 mmol), 4,6,9,12,15,17-hexakis(1,1-dimethy-
lethyl)tetrabenz[bc,ef,hi,uv]ovalene-1,2-dione (28 mg, 0.03 mmol), and
acetic acid (6 mL) was refluxed for 14 h under Ar. After cooling to room
temperature, the solvent was evaporated. The residue was purified by
silica-gel column chromatography (petroleum ether (b.p. 50–708C)/
CH2Cl2 1:1) to give 1 as a dark-purple emissive powder. Yield: 28 mg
(67%); m.p.>3508C (dec.); IR (KBr): n˜ =3450, 2922, 2851, 1637, 1503,
3436, 1742, 1675, 1446, 1203, 874 cmꢀ1 13C NMR (75 MHz, CDCl3): d=
;
1384, 1200, 869 cmꢀ1 1H NMR (300 MHz, CDCl3): d=9.71 (s, 4H), 9.34
;
150.9, 138.0, 132.5, 106.6 ppm; MS (EI): m/z (%): 382 (31) [M+]; elemen-
tal analysis calcd (%) for C7Br2N2OS3: C 21.89, N 7.29; found: C 21.82, N
7.16.
(s, 8H) 9.25 (s, 4H), 8.86 (s, 4H), 7.28 (d, J=8.1 Hz, 8H), 2.63 (t, J=
7.5 Hz, 8H), 1.84 (s, 36H), 1.78 (s, 36H), 1.71 (s, 36H), 1.53 (s, 24H),
0.84 ppm (m, 12H); 13C NMR (75 MHz, CDCl3): d=157.2, 147.0, 145.6,
137.2, 136.1, 133.5, 132.6, 130.7, 130.1, 129.7, 129.2, 119.7, 116.0, 39.2,
35.9, 35.3, 34.6, 32.1, 32.0, 31.9, 29.7, 29.4, 22.7, 14.1 ppm; MS (MALDI-
TOF): m/z calcd for C194H188N4O4S4: 2765.35; found: 2765.44.
4,8-Dibromo-6-(4,8-dibromo
ACHUTGTNRNEUG[N 1,3]dithioloACHTUNGTNER[NUGN 4,5-f]-2,1,3-benzothiadiazol-6-
ylidene)-[1,3]dithiolo[4,5-f]-2,1,3-benzothiadiazole (5)
ACHTUNGTRENNUNG
Triethyl phosphite (2 mL) was added to solution of 4 (60 mg,
a
0.156 mmol) in toluene (2 mL) under Ar. The mixture was refluxed for
3 h. The resulting orange solid was collected and washed with EtOH to
afford 5. Yield: 50 mg (87%); m.p.>3508C (dec.); IR (KBr): n˜ =3435,
2-[4,9-Bis(4-pentylphenoxy)-1,3-dithiolo
ACHTUNGTRENN[UNG 4,5-g]quinoxalin-2-ylidene]-4,9-
bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxaline (8)
AHCTUNGTRENNUNG
1,4-Dioxane-2,3-diol (10.4 mg, 86.5 mmol) was added to a suspension of 2
(35 mg, 34.6 mmol) in EtOH (10 mL) and acetic acid (99%, 2 mL). The
mixture was refluxed for 8 h under Ar and by then a red precipitate was
formed. After filtration, the red powder was purified by column chroma-
tography (basic Al2O3, CH2Cl2) to give 8 as an orange powder. Yield:
19.2 mg (53%); m.p.>3508C (dec.); IR (KBr): n˜ =3437, 3153, 2927,
1477, 1449, 1254, 1238, 1210, 1123, 876, 840 cmꢀ1 13C NMR is unavailable
;
due to poor solubility; MS (MALDI-TOF): m/z calcd for C14Br4N4S6:
731.52; found: 731.52; elemental analysis calcd (%) for
C14Br4N4S6·0.5C2H5OH: C 23.73, H 0.40, N 7.38; found: C 24.11, H 0.09,
N 7.60.
1635, 1506, 1449, 1400, 1383, 1210, 1075, 1029 cmꢀ1 1H NMR (300 MHz,
;
6-[4,8-Bis(4-pentylphenoxy)
ylidene]-4,8-bis(4-pentylphenoxy)
benzothiadiazole (6)
A
ACHTUNGTRENNUNG
CDCl3): d=8.64 (s, 4H), 7.08 (d, J=7.90 Hz, 8H), 6.80 (d, J=7.90 Hz,
8H), 2.54 (t, J=7.1 Hz, 8H), 1.59–1.56 (m, 8H), 1.30–1.29 (m, 16H),
0.87 ppm (t, J=6.6 Hz, 12H); 13C NMR (75 MHz, CDCl3): d=155.2,
144.2, 139.6, 137.5, 137.2, 134.8, 129.6, 115.4, 35.1, 31.4, 31.2, 22.5,
14.0 ppm; MS (MALDI-TOF): m/z calcd for C62H65N4O4S4: 1057.39;
found: 1057.14; elemental analysis calcd (%) for C62H64N4O4S4: C 70.42,
H 6.10, N 5.30; found: C 70.19, H 5.84, N 5.16.
A
ACHTUNGTRENNUNG
A solution of 5 (20 mg, 2.72 mmol), K2CO3 (15 mg, 108.8 mmol), and 4-
pentylphenol (0.03 mL, 175 mmol) in N,N-dimethylformamide (DMF;
1.5 mL) was degassed with Ar and then kept at 1508C under microwave
irradiation for 1 h. The precipitate was collected by centrifuge and
washed with H2O and EtOH several times. The crude product was puri-
fied by silica-gel column chromatography (CH2Cl2/hexane 1:1) to afford
pure compound 6 as an orange solid. Yield: 12 mg (41%); m.p. 273–
2758C; IR (KBr): n˜ =3436, 2955, 2925, 2853, 1606, 1532, 1505, 1478, 1336,
Acknowledgements
1
1200, 1167, 830 cmꢀ1; H NMR (300 MHz, CDCl3): d=7.11 (d, J=8.7 Hz,
8H), 6.85 (d, J=8.7 Hz, 8H), 2.55 (t, J=7.8 Hz, 8H), 1.58 (m, 8H), 1.31
(m, 16H), 0.88 ppm (t, J=6.6 Hz, 12H); 13C NMR (75 MHz, CDCl3): d=
168.3, 154.5, 138.3, 129.6, 116.06, 35.1, 31.5, 31.1, 22.5, 14.0 ppm; MS
(MALDI-TOF): m/z calcd for C58H60N4O4S6 1068.29, found 1068.68; ele-
mental analysis calcd (%) for C58H60N4O4S6·0.5C6H14: C 65.85, H 6.07, N
5.04; found: C 65.61, H 6.20, N 4.73.
This work was supported by the Swiss National Science Foundation
(grant Nos. 200020-130266/1 and 200020-125175). We thank Ursula
Bꢀnzli-Trepp for the kind help with the nomenclature of all new com-
pounds.
[1] a) J. Yamada, T. Sugimoto in TTF Chemistry. Fundamentals and ap-
plications of Tetrathiafulvalene, Springer Verlag, Berlin, 2004; b) D.
2009, 2245; c) P. Batail, (Ed.) Chem. Rev. 2004, 104 special issue No.
11 “Molecular Conductors”; d) J. L. Segura, N. Martꢇn, Angew.
[2] a) P. R. Ashton, V. Balzani, J. Becher, A. Credi, M. C. T. Fyfe, G.
Mattersteig, S. Menzer, M. B. Nielsen, F. M. Raymo, J. F. Stoddart,
121, 3951; b) X. Li, G. Zhang, H. Ma, D. Zhang, J. Li, D. Zhu, J.
2-[5,6-Diamino-4,7-bis(4-pentylphenoxy)-1,3-benzodithiol-2-ylidene]-4,7-
bis(4-pentylphenoxy)-1,3-benzodithiole-5,6-diamine (2)
The suspension of 6 (150 mg, 140 mmol) in a mixture of CH2Cl2 (60 mL)
and EtOH (50 mL) was purged with Ar for several minutes, and then
NaBH4 (280 mg, 7.4 mmol) and CoCl2·6H2O (125 mg, 0.53 mmol) were
added sequentially. Evolution of H2S was observed immediately, and the
color of the solution slowly changed from orange to dark brown. The re-
sulting solution was heated at 408C for 30 min and then was stirred for
another 3 h at room temperature. A significant amount of black precipi-
tate was formed. After filtration, the filtrate was concentrated under
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Chem. Asian J. 2011, 6, 3312 – 3321