Aminophenalenyl-Based Radical Molecular Conductors
A R T I C L E S
(s). Anal. Calcd for C15
H
14
2
N : C, 81.03; H, 6.36; N, 12.60. Found: C,
under reduced pressure and used for the next step without further
8
1.42; H, 6.44; N, 12.51.
purification. MS (MALDI), m/z ) 593.
2
+
-
9-N-Methylamino-5-methyl-1-N′-methylimino-phenalene (L ). Tri-
4
4
Preparation of 8 BPh . A solution of 0.30 g of NaBPh (0.87
+
-
ethyloxonium tetrafluoroborate (1.44 g, 7.6 mmol) was added to a
solution of 9-N-methylamino-5-methyl-1-oxophenalene (1.70 g, 7.6
mmol) in 50 mL dry CH Cl . The solution immediately turned wine-
2 2
red, and then a yellow precipitate formed. The reaction mixture was
mmol) in 10 mL MeOH was added to a solution of 8 Cl , (0.25 g,
0.51 mmol) in 10 mL of MeOH. A red precipitate formed immediately.
The mixture was stirred for 15 min, and the red solid was separated by
filtration and stored in the dark. The crude product can be purified by
recrystallization from dichloromethane/methanol mixture to give red
stirred 2 h at 25 °C, and then methylamine (8 mL 2M solution in MeOH,
1
6 mmol), was added whereupon the yellow precipitate dissolved to
crystals of the title compound (0.3 g, 76%). MS (MALDI), m/z ) 453.
H NMR (CD CN): δ 8.35 (d, 4H), 8.19 (d, 4H), 7.68 (t, 2H), 7.46 (d,
3
1
give a deep red solution. The reaction mixture was stirred at 25 °C for
an additional 6 h. The mixture was poured into 100 mL distilled water;
the organic layer was separated and dried over sodium sulfate. The
solvent was removed with a rotary evaporator to yield a dark red pasty
solid, and this was purified by column chromatography on Al
ethyl ether to give an analytically pure red solid (L ) (1.1 g, 61%). mp
4H), 7.27 (m, 8H), 6.98 (t, 8H), 6.83 (t, 4H), 3.05 (b, 12H). IR (600-
-
1
4000 cm ): 3058(w), 3006(w), 1627(s), 1577(s), 1539(w), 1516(s),
1493(w), 1474(w), 1456(w), 1424(m), 1417(m), 1362(m), 1349(s),
1320(s), 1251(m), 1203(m), 1161(m), 986(s), 901(m), 882(w), 840-
(m), 822(w), 815(w), 763(w), 748(w), 734(s), 705(s). Anal. Calcd for
O
2 3
with
2
1
1
09 °C. H NMR (CDCl
3
): δ12.83 (b, 1H), 7.63 (d, 2H), 7.54 (s, 2H),
54 46 2 4
C H B N : C, 83.95; H, 6.00; N, 7.25. Found: C, 83.71; H, 5.95; N,
-
1
7
.19 (d, 2H), 3.35 (s, 6H), 2.52 (s, 3H). IR (600-4000 cm ): 2963-
6.90.
Preparation of 9 BPh . A solution of 0.5 g of NaBPh (1.46 mmol)
+
-
(
(
w), 2924(w), 2859(w), 1631(m), 1604(vs), 1579(m), 1527(s), 1466-
m), 1399(s), 1362(m), 1312(m), 1276(m), 1170(s), 1120(w), 1074(w),
4
4
+
-
in 10 mL MeOH was added to a solution of 9 Cl , (0.5 g, 0.97 mmol)
in 10 mL of MeOH. A red precipitate formed immediately. The mixture
was stirred for 15 min, and the red solid was separated by filtration
and stored in the dark. The crude product can be purified by
recrystallization from dichloromethane/methanol mixture to give red
1
039(w), 963(m), 930(s), 865(s), 844(w), 813(s), 784(m), 759(w), 744
(w). Anal. Calcd for C16
H
16
2
N : C, 81.32; H, 6.82; N, 11.85. Found:
C, 81.11; H, 6.87; N, 11.77.
3
9
-N-Methylamino-1-N′-hexylimino-phenalene (L ). Triethyloxo-
nium tetrafluoroborate (0.57 g, 3 mmol) was added to a solution of
-N-methylamino-1-oxophenalene (0.63 g, 3 mmol) in 20 mL dry CH
Cl . The solution immediately turned wine-red, and then a yellow
precipitate formed. The reaction mixture was stirred 10 h at 25 °C,
and then hexylamine (0.80 mL, 6 mmol) was added, whereupon the
yellow precipitate dissolved to give a deep red solution. The reaction
mixture was stirred at 25 °C for additional 6 h. The mixture was poured
into 50 mL water; the organic layer was separated and dried over
sodium sulfate. The solvent was removed with a rotary evaporator,
crystals of the title compound (0.57 g, 73%). MS (MALDI), m/z )
1
9
2
-
481. H NMR (CD
3
CN): δ 8.29 (d, 4H), 8.02 (s, 4H), 7.43(d, 4H),
2
7.26 (m, 8H), 6.99 (t, 8H), 6.84 (t, 4H), 3.02 (b, 12H), 2.61 (s, 6H). IR
-
1
(600-4000 cm ): 3010(w), 2971(w), 2928(w), 2869(w), 1633(s),
1593(s), 1522(s), 1483(s), 1424(s), 1372(s), 1343(m), 1326(m), 1316-
(s), 1291(s), 1197(m), 1162(s), 992(s), 969(w), 901(w), 874(m), 826-
(s), 748(m), 734(s), 709(s). Anal. Calcd for C56
50 2 4
H B N : C, 83.99; H,
6.30; N, 6.99. Found: C, 84.01; H, 6.38; N, 7.11.
+
-
Preparation of 10 BPh4 . A solution of 0.72 g of NaBPh (2.1
4
+
-
and the crude product was purified by column chromatography on Al
with ethyl ether to give an analytically pure orange solid (L ) (0.725
2
O
3
mmol) in 10 mL MeOH was added to a solution of 10 Cl , (0.78 g,
1.24 mmol) in 30 mL of MeOH. An orange precipitate formed
immediately. The mixture was stirred for 15 min, and the orange solid
was separated by filtration and stored in the dark. The crude product
can be purified by recrystallization from dichloromethane/methanol
mixture to give red microcrystals of the title compound 0.19 g (17%).
3
1
g, 83%). mp 61 °C. H NMR (CDCl
3
): δ13.33 (b, 1H), 7.63-7.72
m, 4H), 7.28 (t, 1H), 7.21 (d, 1H), 7.20 (d, 1H), 3.60 (m, 2H), 3.35
s, 3H), 1.84 (m, 2H), 1.56 (m, 2H), 1.40 (m, 4H), 0.94 (t, 3H). IR
(
(
(
-
1
600-4000 cm ): 2959(w), 2937(w), 2863(m), 1652(w), 1633(s),
608(s), 1587(m), 1573(m), 1520(s), 1470(m), 1366(s), 1310(m), 1245-
w), 1228(w), 1182(s), 1163(s), 961(w), 919(s), 834(s), 819(s), 757-
m), 738(m), 679(s). Anal. Calcd for C20 : C, 82.13; H, 8.28; N,
.58. Found: C, 82.41; H, 8.46; N, 9.44.
Preparation of 8 Cl . 9-N-Methylamino-1-N′-methylimino-
phenalene (L , 0.31 g, 1.4 mmol) in chlorobenzene (60 mL) was treated
with boron trichloride (0.7 mL 1 M solution in CH Cl , 0.7 mmol)
1
1
(
(
H NMR (CD CN): 8.36 (d, 2H), 8.32 (d, 2H), 8.18 (d, 4H), 7.67 (t,
3
2H), 7.47 (d, 2H), 7.38 (d, 2H), 7.27 (m, 8H), 6.98 (t, 8H), 6.83 (t,
4H), 3.38 (m, 4H), 3.08 (b, 6H), 1.64 (m, 2H), 1.48 (m, 2H), 1.12 (m,
24 2
H N
-
1
9
4H), 0.95 (m, 8H), 0.52 (t, 6H). IR (600-4000 cm ): 3058(w), 2959
(w), 2928(m), 2869(w), 1632(s), 1588(s), 1515(s), 1493(m), 1453(m),
1408(w), 1358(m), 1347(w), 1328(m), 1255(m), 1207(m), 1161(m),
1036(w), 988(m), 961(m), 905(s), 842(s), 821(m), 736(m), 703(s). Anal.
+
-
1
2
2
under argon in the dark, and the mixture was refluxed for 20 h. The
red precipitate was isolated by filtration (0.26 g, 76%). MS (MALDI),
Calcd for C64
H, 7.27; N, 6.23.
Crystallization of 8. An invertible H-cell with a glass D frit was
66 2 4
H B N : C, 84.19; H, 7.30; N, 6.14. Found: C, 83.85;
-
1
m/z ) 453. IR (600-4000 cm ): 3083(w), 2989(w), 2881(w), 1633-
s), 1577(s), 1520(s), 1495(m), 1458(m), 1424(w), 1418(w), 1403(w),
364(w), 1349(s), 1322(m), 1310(m), 1252(m), 1205(m), 1162(s), 990-
+
-
(
1
loaded in a drybox. A solution of 50 mg of 8 BPh4 (0.065 mmol) in
12 mL dry acetonitrile was placed in one container, and 15 mg of CoCp2
(0.080 mmol) dissolved in 12 mL of dry acetonitrile in the other
container. The H-cell was removed from the drybox and attached to
the vacuum line, and the containers were taken through three cycles of
freeze, pump, and thaw to degas the solutions. The H-cell was inverted
slowly, and the solutions were allowed to diffuse through the glass
frit. After sitting in the dark for one week, the cell yielded 17 mg of
(
(
s), 903(m), 884(w), 853(m), 842(s), 822(m), 784(m), 740(m), 690-
m).
+
-
Preparation of 9 Cl . 9-N-Methylamino-5-methyl-1-N′-methylimino-
2
phenalene (L , 0.49 g, 2.1 mmol) in chlorobenzene (50 mL) was treated
with boron trichloride (1.0 mL 1 M solution in CH Cl , 1 mmol) under
2
2
argon in the dark, and the mixture was refluxed for 18 h. The red
-1
precipitate was isolated by filtration (0.48 g, 93%). MS (MALDI), m/z
black shining crystals. IR (600-4000 cm ): 3036(w), 2889(w), 1629-
(m), 1577(m), 1547(m), 1522(w), 1481(m), 1470(m), 1445(w), 1402-
(s), 1362(w), 1351(w), 1324(w), 1257(s), 1205(m), 1170(m), 1130(m),
1114(m), 1078(w), 920(s), 828(m), 805(m), 742(m), 709(w), 688(w),
-
1
)
481. IR (600-4000 cm ): 3003(w), 2920(w), 1631(m), 1591(s),
1524(s), 1481(m), 1458(w), 1420(m), 1366(s), 1347(m), 1318(m), 1289-
(
(
m), 1197(m), 1166(m), 992(s), 969(w), 876(s), 823(m), 788(w), 698-
m), 684(w).
671(w). Anal. Calcd for C30
Found: C, 79.10; H, 6.02; N, 12.33.
Crystallization of 9. An invertible H-cell with a glass D frit was
4
H26BN : C, 79.48; H, 5.78; N, 12.36.
+
-
Preparation of 10 Cl . 9-N-Methylamino-1-N′-hexylimino-
3
phenalene (L , 0.61 g, 2.1 mmol) in toluene (30 mL) was treated with
boron trichloride (1.0 mL 1 M solution in CH Cl , 1 mmol) under argon
+
-
4
(0.14 mmol) in
2
2
loaded in a drybox. A solution of 112 mg of 9 BPh
15 mL dry acetonitrile was placed in one container, and 32 mg of CoCp
(0.17 mmol) was dissolved in 16 mL of dry acetonitrile in the other
in the dark, and the mixture was refluxed for 14 h. The red sticky oil
was separated by decantation of toluene; residual solvent was evaporated
2
J. AM. CHEM. SOC.
9
VOL. 127, NO. 22, 2005 8195