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130.6, 130.1, 129.3, 128.8, 127.5, 127.0, 126.7, 126.1, 33.5,
29.1, 28.5, 22.5, 14.3, 13.7. MS (FAB) m/z 1152.0 (MCC
1). Anal. Calcd for C78H86S4: C, 81.34; H, 7.53; S, 11.13.
Found: C, 81.20; H, 7.62. Mp 280 8C.
133.1, 131.6, 131.1, 130.6, 130.0, 129.8, 128.7, 127.5,
126.9, 126.6, 126.5, 122.9, 122.5. MS (FAB) m/z 1087.5
(MC). Anal. Calcd for C86H54: C, 94.99; H, 5.01. Found: C,
95.05; H, 4.98. Mp 414 8C.
4.1.4. 1,2,4,5-Tetrakis[(40-diphenylamino)biphenyl-4-
yl]benzene 5. The synthetic procedure of 4 was followed
using 4-diphenylaminophenylboronic acid (361 mg,
1.25 mmol) and 1,2,4,5-tetrakis(p-iodophenyl)benzene 3
(221 mg, 0.25 mmol). The pure product was separated by
silica gel column chromatography using 6:1 petroleum
ether–dichloromethane as eluent affording 261 mg (77%) of
4.1.8. 1,2,4,5-Tetrakis[20-diphenylamino-90,90-bis(n-
butyl)-70-fluorenyl]benzene 9. To a mixture of 1,2,4,5-
tetrabromobenzene, 5 (76 mg, 0.19 mmol), 9,9-bis(n-butyl)-
2-diphenylamino-7-fluorenylboronic acid (570 mg,
1.14 mmol), Pd(OAc)2 (8.5 mg, 5 mol%) and tri(o-tolyl)-
phosphine (23 mg, 10 mol %) in a 100 mL round-flask were
added toluene (10 mL), methanol (5 mL) and 2 M aqueous
solution of K2CO3 (2.5 mL). The reaction mixture was
stirred under a nitrogen atmosphere at 75 8C for overnight.
After cooling to room temperature, the reaction mixture was
poured into cool water and extracted with dichloromethane
(3!50 mL). The combined organic layer was dried with
anhydrous Na2SO4 and evaporated to dryness. The crude
product was then purified by column chromatography with
petroleum ether–dichloromethane (v/vZ4:1) as eluent
affording the desired product as a white solid (270 mg,
1
a milky white solid. H NMR (400 MHz, CDCl3, d) 7.62
(s, 2H), 7.47 (d, JZ7.20 Hz, 14H), 7.31 (d, JZ7.20 Hz,
8H), 7.24 (t, JZ7.20 Hz, 18H), 7.10 (d, JZ7.60 Hz, 24H),
7.01 (t, JZ7.00 Hz, 8H). 13C NMR (100 MHz, CDCl3, d)
147.6, 147.2, 139.5, 139.3, 138.7, 134.5, 133.0, 130.3,
129.2, 127.6, 126.1, 124.3, 124.0, 122.9. MS (FAB) m/z
1355.9 (MC). Anal. Calcd for C102H74N4: C, 90.37; H, 5.50;
N, 4.13. Found: C, 90.27; H, 5.58; N, 4.29. Mp 301 8C.
1
77% yield). H NMR (400 MHz, CDCl3, d) 7.69 (s, 2H),
4.1.5. 1,2,4,5-Tetrakis[4-(1-naphthyl)phenyl-1-yl] ben-
zene 6. The synthetic procedure of 4 was followed using
1-naphthylboronic acid (516 mg, 3 mmol) and 1,2,4,5-
tetrakis(p-iodophenyl)benzene 3 (443 mg, 0.50 mmol).
The pure product was separated by silica gel column
chromatography using 4:1 petroleum ether–dichloro-
methane as eluent affording 250 mg (56%) of a white
7.46 (t, JZ7.0 Hz, 8H), 7.28 (d, JZ7.6 Hz, 4H), 7.22 (t, JZ
7.6 Hz, 20H), 7.10 (d, JZ7.6 Hz, 16H), 7.05 (s, 4H), 6.98
(dd, JZ7.2 Hz, 12H), 1.69–1.70 (m, 16H), 0.93–0.99 (m,
16H), 0.67 (t, JZ7.0 Hz, 40H). 13C NMR (100 MHz,
CDCl3, d) 152.2, 150.5, 148.0, 146.9, 140.1, 139.5, 139.2,
136.0, 133.4, 129.1, 128.8, 124.4, 123.7, 123.3, 122.4,
120.4, 119.3, 118.7, 54.8, 39.9, 26.1, 22.9, 14.0. MS (FAB)
m/z 1852.8 (MC). HRMS (ESI-MS) calcd for C138H138N4:
1853.1032 (MCC1). Found: 1853.0970.
1
solid. H NMR (400 MHz, CDCl3, d) 7.94 (d, JZ8.40 Hz,
4H), 7.90 (d, JZ8.40 Hz, 4H), 7.86 (d, JZ6.80 Hz, 4H),
7.85 (s, 2H), 7.52 (m, 8H), 7.46 (m, 20H), 7.38 (t, JZ
7.60 Hz, 4H). 13C NMR (100 MHz, CDCl3, d) 140.0, 139.9,
139.7, 139.2, 133.8, 133.0, 131.6, 129.9, 129.8, 128.3,
127.7, 126.9, 126.1, 125.9, 125.7, 125.4. MS (FAB) m/z
886.7 (MCK1). Anal. Calcd for C70H46: C, 94.77; H, 5.23.
Found: C, 94.60; H, 5.36. Mp 286 8C.
4.1.9. Bis(4-n-hexylsulfanyl-1-yl)pentaphenyl 40. A mix-
ture of bis(p-iodophenyl)benzene, 30 (443 mg, 0.5 mmol),
palladium (II) acetate (22 mg, 0.1 mmol), tri(o-tolyl)phos-
phine (61 mg, 0.2 mmol), toluene (30 mL), methanol
(15 mL), 2 M K2CO3 (3 mL), and 4-(n-hexylsulfanyl)-
phenylboronic acid (370 mg, 1.5 ) was heated at 75 8C for
3–4 h under a nitrogen atmosphere with good stirring. After
the reaction mixture was cooled to room temperature, it
was poured into water and extracted with dichloromethane
(3!50 mL). The combined organic layer was dried with
anhydrous Na2SO4 and evaporated to dryness. The crude
product was purified by silica gel column chromatography
using dichloromethane as eluent affording a white solid
(256 mg) with an isolated yield of 88%. 1H NMR
(400 MHz, CDCl3, d) 7.67–7.21 (m, 20H), 2.97 (t, JZ
7.20 Hz, 4H), 1.67–1.71 (m, 4H), 1.46–1.43 (m, 4H), 1.29–
1.32 (m, 8H), 0.89 (t, JZ6.00 Hz, 6H). MS (FAB) m/z 583.9
(MCC1). Anal. Calcd for C78H86S2: C, 86.55; H, 7.95; S,
11.00. Found: C, 86.38; H, 8.05; S, 10.95. Mp 187 8C.
4.1.6. 1,2,4,5-Tetrakis[40-(900-anthryl)phenyl-10-yl] ben-
zene 7. The synthetic procedure of 4 was followed using
9-anthracylboronic acid (400 mg, 1.8 mmol) and 1,2,4,5-
tetrakis(p-iodophenyl)benzene, 3 (266 mg, 0.30 mmol). The
pure product was separated by silica gel column chroma-
tography using 4:1 petroleum ether–dichloromethane as
1
eluent affording 250 mg (77%) of a yellow solid. H NMR
(400 MHz, CDCl3, d) 8.51 (s, 4H), 8.05 (t, JZ8.80 Hz,
10H), 7.74 (d, JZ8.80 Hz, 4H), 7.70 (d, JZ8.00 Hz, 8H),
7.47 (d, JZ8.40 Hz, 8H), 7.39 (t, JZ7.60 Hz, 10H), 7.17
(t, JZ8.00 Hz, 10H). MS (FAB) m/z 1086.5 (MCK1).
Anal. Calcd for C86H54: C, 94.99; H, 5.01. Found: C, 94.92;
H, 5.19. Mp 352 8C.
4.1.7. 1,2,4,5-Tetrakis[40-(900-phenanthryl)phenyl-10-yl]
benzene 8. The synthetic procedure of 4 was followed
using 9-phenanthrylboronic acid (400 mg, 1.8 mmol)
and 1,2,4,5-tetrakis(p-iodophenyl)benzene, 3 (266 mg,
0.30 mmol). The pure product was separated by silica gel
column chromatography using 4:1 petroleum ether–
dichloromethane as eluent affording 250 mg (77%) of a
4.1.10. Bis(4-diphenylamino-1-yl)pentaphenyl 50. The
synthetic procedure of 40 was followed using 4-diphenyl-
aminophenylboronic acid (1.68 g, 5.84 mmol) and bis(p-
iodophenyl)benzene, 30 (936 mg, 1.94 mmol). The pure
product was separated by silica gel column chromatography
using petroleum ether–dichloromethane as gradient eluent
1
1
light-yellow solid. H NMR (400 MHz, CDCl3, d) 8.78 (d,
affording 1261 mg (91%) of a milky white solid. H NMR
JZ8.00 Hz, 4H), 8.72 (d, JZ7.60 Hz, 4H), 7.97 (d, JZ
8.00 Hz, 4H), 7.90 (d, JZ4.80 Hz, 6H), 7.75 (s, 4H), 7.63
(m, 12H), 7.55 (d, JZ2.40 Hz, 12H), 7.49 (m, 8H). 13C
NMR (100 MHz, CDCl3, d) 140.1, 139.8, 139.3, 138.5,
(400 MHz, CDCl3, d) 7.73 (d, JZ3.60 Hz, 4H), 7.70 (d,
JZ8.40 Hz, 4H), 7.65 (d, JZ8.40 Hz, 4H), 7.52 (d, JZ
8.40 Hz, 4H), 7.27 (t, JZ8.40 Hz, 8H), 7.15 (m, 12H), 7.03
(t, JZ7.40 Hz, 4H). 13C NMR (100 MHz, CDCl3, d) 147.6,