Çiçek et al.: Synthesis and optical characterization of bipod carbazole derivativesꢁ
ꢁ151
(
aromatic C-H, out-of-plane, symmetric bending). stretch, naphthalene), 1600 (carbazole C=C stretch),
1
H NMR (CDCl , δ, ppm): 3.475 (2H, s), 3.832 (2H, t), 1467 (aliphatic C-H bend, asymmetric), 1454 (carbazole
3
4
.429 (2H, t), 7.526 (1H, d), 8.107 (1H, m), 7.612 (1H, m), ring stretch), 1291 (aliphatic C-H bend, symmetric), 1120
7
.612 (1H, d), 7.406 (1H, s), 7,412 (1H, d), 7.390 (1H, s). (C-O-C asymmetric bend), 1075 (aliphatic C-H bend,
1
3
C NMR (CDCl , δ, ppm): 69.323, 70.527, 58.602, 130.514, out-of-plane), 1057 (C-N bend), 1030 (C-O-C symmetric
3
1
23.191-110.632, 143.323, 139.551, 128.380, 128.959, 129.081. bend), 801 and 780 (aromatic symmetric C-H bending on
Anal. Calc. for C H N O (MW=752.34): C, 86.14; H, 5.89; α-substituted naphthalene, out-of-plane), 757 and 698
5
4
44
2
2
1
N, 3.72. Found: C, 86.00; H, 5.81; N, 3.77%. LC-MS (m/z): (aromatic symmetric carbazole bend, out-of-plane). H
7
+
53.30 (M , CH CN, Error % = 0.128).
NMR (CDCl δ, ppm): 3.388 (4H, s), 3.498 (2H, t), 3.635 (2H, t),
3
3,
7
.262 (1H, d), 7.590 (1H, d), 7.608 (1H, d), 7.539 (1H, d),
7
.281 (1H, s), 8.060 (1H, m), 7.222-7.135 (2H, m), 7.467 (1H,
1
3
Synthesis of Bis[2-(2-(3,6-diphenyl-9H-carbazole-9-yl)
ethoxy)etyl]ether(C-2)
m), 7.498 (1H, m), 7.377 (1H, d), 7.940 (1H, d). C NMR
(CDCl , δ, ppm): 74.010-72.125, 61.406, 133.150, 125.332,
3
125.759, 141.253, 126.505, 125.926, 138.408, 132.807, 128.106,
C-2 was obtained from bis[2-(2-(3,6-dibromo-9H-carbazole- 127.854, 133.485, 128.185, 127.786. Anal. Calc. for C H N O
9
72
56
2
3
-yl)ethoxy)etyl]ether (C-a2) (0.2 mmol, 0.16 g), PhB(OH) (MW=996.43): C, 86.72; H, 5.66; N, 2.81. Found: C, 86.68;
2
+
(
0.8 mmol, 0.098 g) and Pd (dba) (0.06 mmol, 0.055 g) H, 5.60; N, 2.90. %. LC-MS (m/z): 996.43 (M , CH CN,
2
3
3
and K CO (aq., 2M, 3 ml), toluene (6 ml) following the Error % = 0.003).
2
3
General Procedure-II. The yellow-green, slightly oily solid
was recrystallized from ethanol (0.127 g, 80.3%). FT-IR
-1
(
γcm ):3055(aromaticC-Hstretch),2924and2855(aliphatic Synthesis of Bis[2-(2-(3,6-di(naphthalene-2-yl)-9H-
C-H, symmetric and asymmetric stretch), 1596 (aromatic carbazol-9-yl)ethoxy)ethyl]ether(C-4)
C=C stretch), 1470 (aliphatic C-H bend, asymmetric),
1
448 (carbazole ring stretch), 1343 (aliphatic C-H bend, C-4 was obtained from bis[2-(2-(3,6-dibromo-9H-carba-
symmetric), 1139 (C-O-C asymmetric bend), 1112 (aliphatic zole-9-yl)ethoxy)etyl]ether (C-a2) (0.06 mmol, 0.048 g),
C-H bend, out-of-plane), 1055 (C-N bend), 1018 (C-O-C 2-naphthylboronic acid (0.24 mmol, 0.041 g) and
symmetric bend), 740 and 701 (aromatic C-H bend, out-of- Pd (dba) (0.0018 mmol, 0.0016 g) were placed in a
2
3
1
plane, symmetric). H NMR (CDCl , δ, ppm): 3.472 (4H, s), 100 ml flask, then quickly K CO (aq., 2M, 9 ml), toluene
3
3
2
3
.810 (2H, t), 4.291 (2H, t), 7.619 (1H, d), 8.074 (1H, d), 8.089- (18 ml) following the General Procedure-II. The light-
8
.106 (1H, d), 8.040 (1H, d), 7.601 (1H, s), 7.401 (1H, s), brown, slightly oily solid was recrystallized from
13
-1
7
.417 (1H, d), 7.333 (1H, m). C NMR (CDCl , δ, ppm): 70.535, ethanol (0.048 g, 81.6%). FT-IR (γ cm ): 3054 and 3022
3
6
9.301, 70.901, 60.644, 131.885, 110.831, 123.434 143.323, (aromatic C-H stretch), 2923 and 2854 (symmetric and
23.945, 123.023, 139.521, 128.395, 128.974, 127.237. Anal. asymmetric aliphatic C-H stretch), 1624, 1569 and 1494
1
Calc. for C H N O (MW=796.37): C, 84.39; H, 6.07; N, 3.51. (aromatic C=C stretch, naphthalene), 1594 (carbazole
56
48
2
3
Found: C, 84.36; H, 6.01; N, 3.55%. LC-MS (m/z): 796.40 C=C stretch), 1467 (aliphatic C-H bend, asymmetric),
+
(
M , CH CN, Error % = 0.004).
1454 (cbz ring stretch), 1290 (C-H aliphatic, in-plane,
symmetric), 1131 (C-O-C asymmetric bend), 1076 (ali-
phatic C-H bend, out-of-plane), 1031 (C-O-C symmetric
stretch), 811 and 737 (aromatic symmetric C-H bend on
β-substituted naphthalene, out-of-plane), 748 and 699
3
Synthesis of Bis[2-(2-(3,6-di(naphthalene-1-yl)-9H-
carbazol-9-yl)ethoxy)etyl]ether(C-3)
(
aromatic symmetric C-H bend on carbazole benzene,
1
C-3 was obtained from bis[2-(2-(3,6-dibromo-9H-carbazole- out-of-plane,). H NMR (CDCl , δ, ppm): 3.287 (4H, s),
3
9
-yl)ethoxy)etyl]ether (C-a2) (0.04 mmol, 0.032 g), 3.725 (2H, t), 4.379 (2H, t), 7.218 (1H, d), 7.927 (1H, s),
naphthalene-1-boronic acid (0.16 mmol, 0.028 g) and 7.900 (1H, d), 8.122-8.059 (1H, d), 7.258 (1H, s), 7.514 (2H,
1
3
Pd (dba) (0.0012 mmol, 0.001 g) were placed in a 100 ml m), 7.279 (2H, s), 7.952 (1H, d), 7.361 (1H, d). C NMR
flask, then quickly K CO (aq., 2M, 6 ml), toluene (12 ml) (CDCl , δ, ppm): 70.548, 70.650, 125.332, 125.759, 61.434,
2
3
2
3
3
following the General Procedure-II. The light-brown, 133.757, 125.718, 126.099, 143.210, 126.381, 126.030,
slightly oily solid was recrystallized from ethanol (0.024 g, 138.398, 127.684, 133.510, 128.537, 132.675, 128.233. Anal.
-
1
6
1.3%). FT-IR (γ cm ): 3062 and 3026 (aromatic C-H Calc. for C H N O (MW=996.43): C, 86.72; H, 5.66; N,
72 56 2 3
stretch), 2923 and 2854 (aliphatic C-H stretch, asymmetric 2.81. Found: C, 86.65; H, 5.63; N, 2.85 %. LC-MS (m/z):
and symmetric), 1656, 1579 and 1496 (aromatic C=C 996.43 (M , CH CN, Error % = 0.003).
+
3