10.1002/asia.201801784
Chemistry - An Asian Journal
FULL PAPER
(C17H16N4O3Na) m/z 347.1115; Found 347.1109. Elemental analysis calcd
for C17H16N4O3·0.3CH3COOCH2CH3: C, 62.52; H, 5.19; N, 16.38. Found:
C, 62.70; H, 5.20; N, 16.46.
md), 1215 (sh, md), 1177 (sh, md), 1127 (sh, str), 1065 (sh, md), 1007 (sh,
md).
PbL1(CF3SO3)2.
A mixture of L1 (0.096 g, 0.26 mmol) and
L1. A solution of 3 (1.26 g, 8.22 mmol) and 1 (0.505 g, 3.74 mmol) in EtOH
(50 mL) was heated at reflux for 4 h. The yellow mixture was cooled to RT.
The yellow precipitate was filtered, washed with EtOH and Et2O then dried
under vacuum to give L1 (0.833 g, 2.05 mmol, 55%) as a yellow solid. 1H
NMR (400 MHz, [D6]DMSO) δ 8.18 (dd, J = 2.2, 0.9 Hz, 2H, H-11), 7.94
(m, 2H, H-3), 7.86 (dd, J = 8.8, 6.8 Hz, 1H, H-4), 7.77 (s, 2H, H-5), 7.74
(dd, J = 8.7, 0.9 Hz, 2H, H-13/14), 7.70 (dd, J = 8.8, 2.2 Hz, 2H, H-13/14),
4.46 (d, J = Hz, 4H, H-15), 3.67 (d, J = 0.8 Hz, 6H, H-8) ppm. Selected IR
v/cm-1: 3288 (br str, O-H), 3002 (sh, wk, N-H), 2867 (sh, wk, N-H), 1604
(sh, str), 1582 (sh, str), 1562 (sh, str, C=N), 1487 (sh, str), 1455 (sh, str),
1397 (sh, str), 1370 (sh, str), 1311 (sh, str), 1283 (sh, md), 1232 (sh, md),
1202 (sh, str), 1153 (sh, md), 1144 (sh, md), 1116 (sh, str), 1032 (sh, str),
1014 (sh, str). HR-ESI-MS: Calcd for [L1+Na]+ (C21H23N7O2Na) m/z
Pb(CF3SO3)2·H2O (0.322 g, 0.616 mmol) in CH3CN (25 mL) was stirred at
RT for 5 h and the orange solution evaporated in vacuo to an orange solid.
The solid was dissolved in CH3CN (25 mL) and vapour diffused with Et2O
(50 mL) to give PbL1(CF3SO3)2 (0.026 g, 0.029 mmol, 12%) as an orange
solid. 1H NMR (500 MHz, [D4]methanol): δ 8.55 (m, 2H, H-5/11), 8.32 (m,
1H, H-4), 8.00 (m, 2H, H-3/13), 7.51 (d, J = 8.7 Hz, H-14), 4.77 (s, 4H, H-
15), 3.80 (d, J = 0.8 Hz, 3H, H-8) ppm. 13C NMR (126 MHz, [D4]methanol):
δ 155.4 (C-9), 153.4 (C-2), 145.9 (C-11), 142.7 (C-12), 141.1 (C-13), 137.4
(C-5), 133.3 (C-3), 128.1 (C-4), 111.5 (C-14), 61.9 (C-15), 34.8 (C-8) ppm.
Selected IR v/cm-1: 3259 (br, wk, OH), 1598 (sh, md), 1547 (sh, md, C=N),
-
1496 (sh, md), 1401 (sh, md), 1315 (sh, md), 1238 (br, str, SO3CF3 ), 1156
(sh, str), 1127 (sh, str), 1023 (sh, str). HR-ESI-MS: Calcd for
[L1+Pb+CF3SO3]+ (C22H23F3N7O5PbS) m/z 762.1196; Found 762.1233.
Elemental analysis calcd for C23H23F6N7O8PbS2: C, 30.33; H, 2.55; N,
10.77. Found: C, 30.37; H, 2.47; N, 10.82. Single crystals of
[PbL1(CF3SO3)2]·CHCl3 were obtained by vapour diffusion of CHCl3 into a
solution of L1 and two equivalents of Pb(CF3SO3)2·H2O in CH3OH.
428.1811;
Found
428.1772.
Elemental
analysis
calcd
for
C21H23N7O2·0.3H2O: C, 61.39; H, 5.79; N, 23.86. Found: C, 61.24; H, 5.74;
N, 23.54.
L2. A solution of 4 (0.227 g, 1.48 mmol) and 1 (0.101 g, 0.747 mmol) in
EtOH (50 mL) was heated at reflux for 2 h. The white mixture was cooled
to RT. The white precipitate was filtered, washed with EtOH and Et2O then
dried under vacuum to give L2 (0.207 g, 0.503 mmol, 68%) as a white solid.
1H NMR (400 MHz, [D]chloroform) δ 7.94 (d, J = 7.8 Hz, 2H H-3), 7.80 (s,
2H, H-5), 7.64 (m), 7.52 (s), 7.00 (s), 6.77 (d, J = 6.6 Hz, 2H, H-12), 4.70
(d, J = 4.70 Hz, 4H, H-15), 3.74 (s, 6H, H-8) ppm. Selected IR v/cm-1: 3316
(br, wk, O-H), 1592 (sh, str), 1572 (sh, str, C=N), 1483 (sh, str), 1458 (sh,
str), 1378 (sh, str), 1317 (sh, wk), 1291 (sh, wk), 1250 (sh, md), 1218 (sh,
md), 1142 (sh, str), 1082 (sh, wk), 1066 (sh, md), 1028 (sh, md), 1010 (sh,
str). HR-ESI-MS: Calcd for [L2+Na]+ (C21H23N7O2Na) m/z 428.1805;
Found 428.1787. Elemental analysis calcd for C21H23N7O2·0.4H2O: C,
61.12; H, 5.81; N, 23.76. Found: C, 61.06; H, 5.39; N, 23.48.
L3. A mixture of 2 (0.571 g, 4.16 mmol) and 6 (0.424 g, 1.07 mmol) in
EtOH (50 mL) was heated at reflux for 1 h. The yellow mixture was cooled
to RT. The yellow precipitate was filtered, washed with EtOH and Et2O
then dried under vacuum to give L3 (0.359 g, 0.565 mmol, 53%) as a
yellow solid. Selected IR v/cm-1: 3164 (br, md, O-H), 1563 (sh, str), 1547
(sh, str, C=N), 1499 (sh, wk), 1476 (sh, md), 1455 (sh, str), 1443 (sh, str),
1398 (sh, str), 1264 (sh, md), 1229 (sh, str), 1133 (sh, str), 1123 (sh, str),
1035 (sh, md), 1007 (sh, md). HR-ESI-MS: Calcd for [L3+Na]+
(C37H33N9O2Na) m/z 658.2649; Found 658.2618. Elemental analysis calcd
for C37H33N9O2·1.5H2O: C, 67.05; H, 5.48; N, 19.02. Found: C, 67.64; H,
5.12; N, 18.80.
PbL2(CF3SO3)2.
A mixture of L2 (0.058 g, 0.14 mmol) and
Pb(CF3SO3)2·H2O (0.112 g, 0.214 mmol) in CH3CN (25 mL) was stirred at
RT for 30 min, filtered, and a 1:1 mixture of PE/Et2O (150 mL) added to
the filtrate to give PbL2(CF3SO3)2 (0.082 g, 0.090 mmol, 63%) as a yellow
solid. 1H NMR (500 MHz, [D4]methanol): δ 8.44 (d, J = 1.1 Hz, 2H, H-5),
8.19 (t, J = 7.8 Hz, 1H, H-4), 7.90 (dd, J = 8.5, 7.5 Hz, 2H, H-13), 7.82 (d,
J = 7.8 Hz, 2H, H-3), 7.27 (d, J = 8.5 Hz, 2H, H-14), 7.07 (dd, J = 7.4, 0.9
Hz, 2H, H-12), 4.96 (s, 4H, H-15), 3.74 (d, J = 0.9 Hz, 6H, H-8) ppm. 13
C
NMR (126 MHz, [D4]methanol): δ 160.3 (C-11), 156.8 (C-9), 154.2 (C-2),
141.8 (C-13), 141.6 (C-4), 138.8 (C-5), 127.4 (C-3), 116.0 (C-12), 109.4
(C-14), 65.3 (C-15), 34.8 (C-8) ppm. Selected IR v/cm-1: 3335 (sh, br, O-
H), 1589 (sh, md), 1548 (sh, md, C=N), 1481 (sh, md), 1433 (sh, md), 1328
-
(sh, str), 1287 (sh, str), 1221 (br, str, SO3CF3 ), 1166 (sh, md), 1019 (sh,
str). HR-ESI-MS: Calcd for [L2+Pb+CF3SO3]+ (C22H23F3N7O5PbS) m/z
762.1196; Found 762.1268. Calcd for [L2+Pb-H]+ (C21H22N7O2Pb) m/z
612.1598;
C23H23F6N7O8PbS2: C, 30.33; H, 2.55; N, 10.77. Found: C, 30.38; H, 2.42;
N, 10.70. Single crystals of
PbL2(CF3SO3)2][PbL2CF3SO3]CF3SO3·CH3CN were obtained by vapour
diffusion of Et2O into solution of L2 and one equivalent of
Pb(CF3SO3)2·H2O in CH3CN.
Pb2L3(CF3SO3)4. mixture of L3 (0.025 g, 0.039 mmol) and
Found
612.1651.
Elemental
analysis
calcd
for
a
A
Pb(CF3SO3)2·H2O (0.085 g, 0.16 mmol) in CH3CN (25 mL) was stirred at
RT for 1 h and the yellow solution evaporated in vacuo to a yellow solid.
The solid was dissolved in CH3CN (5 mL) and vapour diffused with Et2O
to give Pb2L3(CF3SO3)4 (0.026 g, 0.016 mmol, 41%) as a yellow solid. 1H
NMR (500 MHz, [D3]acetonitrile): δ 8.52 (s, 1H, H-18), 8.45 (s, 1H, H-3),
8.24 (dd, J = 8.6, 7.5 Hz, 1H, H-9), 8.06 (t, J = 7.8 Hz, 1H, H-23), 8.02 (m,
1H, H-12/13/14), 7.96 (d, J = 7.5 Hz, 1H, H-10), 7.74 (dd, J = 7.7, 1.1 Hz,
1H, H-24), 7.63 (m, 2H, H-12/13/14), 7.55 (d, J = 8.7 Hz, 1H, H-8), 7.47 (d,
J = 7.9 Hz, 1H, H-22), 4.91 (d, J = 4.5 Hz, 2H, H-25), 4.87 (m, 1H, H-26),
3.71 (d, J = 0.8 Hz, 4H, H-16) ppm. 13C NMR (126 MHz, [D3]acetonitrile):
δ 161.9 (C-21), 157.5 (C-2), 156.6 (C-7), 155.0 (C-5), 154.3 (C-11), 151.3
(C-19), 143.3 (C-9), 141.5 (C-23), 141.0 (C-18), 137.5 (C-4), 131.5 (C-14),
130.5 (C-12/13), 128.7 (C-12/13), 126.6 (C-24), 124.7 (C-3), 124.0 (C-22),
120.2 (C-10), 118.3 (C-8), 65.1 (C-25), 36.5 (C-16) ppm. Selected IR v/cm-
1: 3420 (br, wk, O-H), 1595 (sh, md), 1574 (sh, md, C=N), 1562 (sh, md),
L4. A solution of 7 (0.253 g, 0.937 mmol) and 6 (0.171 g, 0.430 mmol) in
EtOH (50 mL) was heated at 50 °C for 21 h. The brown mixture was cooled
to RT. The brown precipitate was filtered, washed with EtOH and Et2O then
dried under vacuum to give L4 (0.279 g, 0.309 mmol, 72%) as a brown
solid. Selected IR v/cm-1: 3253 (br, wk, O-H), 2866 (sh, wk), 1605 (sh, str),
1561 (sh, str), 1547 (sh, str, C=N), 1485 (sh, str), 1440 (sh, str), 1392 (sh,
str), 1367 (sh, str), 1308 (sh, md), 1273 (sh, md), 1236 (sh, md), 1216 (sh,
md), 1149 (sh, md), 1110 (sh, str), 1004 (sh, str). Elemental analysis calcd
for C51H47N15O2·CH3CH2OH·1.5H2O: C, 65.28; H, 5.79; N, 21.55. Found:
C, 65.33; H, 5.71; N, 21.40.
L5. A solution of 9 (0.475 g, 1.47 mmol) and 6 (0.258 g, 0.649 mmol) in
THF (50 mL) was heated at reflux for 22 h. The yellow mixture was cooled
to RT. The yellow precipitate was filtered, washed with THF then dried
under vacuum to give L5 (0.399 g, 0.395 mmol, 61%) as a yellow solid. 1H
NMR (400 MHz, [D]chloroform) δ 8.68 (s), 8.27 (m), 7.96 (dd, J = 17.6, 7.8
Hz), 7.88 (d, J = 7.3 Hz), 7.85 (m), 7.80 (s), 7.76 (t, J = 7.8 Hz), 7.70 (d, J
= 8.5 Hz), 7.61 (m), 7.52 (s), 7.00 (s), 6.89 (d, J = 7.1 Hz), 6.52 (dd, J =
17.4, 1.5 Hz, H-38a/b), 6.25 (dd, J = 17.3, 10.4 Hz, H-37), 5.91 (dd, J =
10.4, 1.4 Hz, H-38a/b), 5.25 (s, H-35), 3.90 (s, H-16/28), 3.72 (s, H-16/28)
ppm. Selected IR v/cm-1: 1728 (sh, str, C=O), 1562 (sh, str), 1546 (sh, str,
C=N), 1476 (sh, str), 1435 (sh, str), 1397 (sh, str), 1317 (sh, str), 1252 (sh,
-
1483 (sh, md), 1460 (sh, md), 1209 (br, str, SO3CF3 ), 1165 (sh, str), 1015
(sh,
str).
HR-ESI-MS:
Calcd
for
[L3+Pb2+CF3SO3-H]2+
(C38H32F3N9O5Pb2S) m/z 599.5864; Found 599.5812. Calcd for [L3+Pb]2+
(C37H33N9O2Pb) m/z 421.6259; Found 421.6228. Calcd for [L3+Pb2-2H]2+
(C37H31N9O2Pb2) 524.6066; Found 524.6024. Calc for [L3+Pb2+Br-H]2+
(C37H32BrN9O2Pb2) 564.5686; Found 564.5643. Elemental analysis calcd
for C41H33F12N9O14Pb2S4: C, 29.91; H, 2.02; N, 7.66. Found: C, 30.11; H,
2.14; N, 7.40. Single crystals of [Pb2L3(CF3SO3)2Br]CF3SO3·CH3CN were
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