CHEMPLUSCHEM
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1
3
30.5, 130.1, 129.5, 128.7, 127.9, 127.5, 124.5 ppm; IR (KBr): n˜ =
Experimental Section
442, 3325, 2774, 2464, 1712, 1644, 1583, 1541, 1451, 1380, 1222,
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1
Materials and methods
1144, 1077, 994, 897, 835, 783, 741, 682, 635, 487 cm ; elemental
analysis calcd (%) for C H N O (442.39): C 62.45, H 3.19, N 12.66;
found: C 62.69, H 3.22, N 12.45.
23
14
4
6
The H L ligand was prepared according to the literature with some
3
[24–27]
modifications (Scheme 1).
All other chemicals were obtained
from commercial sources without further purification. Elemental
analyses (C, H, and N) were recorded on an Elementar Vario EL III
Synthesis of 1–4 and 7: In a typical reaction, a mixture of
NdCl ·6H O (0.25 mmol) and H L (0.25 mmol) was placed in
3
2
3
1
13
elemental analyzer. H and C NMR spectra were recorded at room
temperature by using a Varian Inova 400 MHz apparatus and tetra-
methylsilane (TMS) as a reference. The IR spectra were recorded as
KBr pellets on a Bruker EQUINOX 55 Fourier transform infrared
a Teflon-lined stainless-steel vessel (25 mL) with DMF/H O (3:7, v/v,
2
10 mL). The mixture was heated to 1608C over the course of 6 h
and maintained at this temperature for 3 days. After cooling to
ꢀ1
room temperature at a rate of 58Ch , yellow block crystals of 2
were obtained (yield 49% based on NdCl ·6H O). IR (KBr) for 2: v˜ =
ꢀ1
spectrometer in the range of 400–4000 cm . The emission spectra
were recorded on a Hitachi F-4500 spectrophotometer in the solid
state at room temperature. TGA was performed with a Universal
3
2
3419, 1618, 1585, 1424, 1371, 1268, 1228, 1173, 1082, 1007, 923,
ꢀ1
854, 790, 733, 706, 657, 628, 551 cm ; elemental analysis calcd (%)
for C H N O Nd (1183.21): C 46.70, H 1.87, N 9.47; found: C
V2.6 DTA instrument under an N atmosphere at a heating rate of
2
46 22
8
13
2
ꢀ
1
1
08Cmin .
46.95, H 1.89, N 9.36.
Yellow block crystals of 1, 3, 4, and 7 were obtained in moderate
yields (36%–63%) by a similar method to that described for 2,
except that the corresponding LnCl ·6H O was used instead of
Synthesis
’-(4-N-oxypyridyl)-2,2’:6’,2“-terpyridine-1,1”-di-N-oxide: 4’-Pyrid-
3
2
4
NdCl ·6H O. For 1: IR (KBr): v˜ =3419, 1618, 1585, 1424, 1371, 1268,
3 2
ꢀ1
yl-2,2’:6’,2“-terpyridine (0.93 g, 3 mmol) and mCPBA (0.774 g,
1228, 1173, 1082, 1007, 923, 854, 790, 733, 706, 657, 628, 551 cm
;
4
.5 mmol) in CH Cl (80 mL) were stirred at room temperature for
elemental analysis calcd (%) for C H N O Pr (1176.54): C 46.96, H
2 2
46 22
8
13
2
2
4 h. Yellow precipitate was filtered off, recrystallized with ethanol
1.88, N 9.52; found: C 47.14, H 1.91, N 9.67. For 3: IR (KBr): v˜ =
and DMF, and dried in vacuo to yield a yellow powder (0.79 g,
3419, 1618, 1585, 1424, 1371, 1268, 1228, 1173, 1082, 1007, 923,
854, 790, 733, 706, 657, 628, 551 cm ; elemental analysis calcd (%)
1
ꢀ1
7
1
4
8
1
4%). M.p. 245–2468C; H NMR (400 MHz, [D ]DMSO): d=9.10 (s,
6
H), 8.44 (d, J=12.0 Hz, 1H), 8.38 (d, J=8.0 Hz, 1H), 8.22 (d, J=
.0 Hz, 8.0 Hz, 1H), 7.91 (d, J=8.0 Hz, 2H), 7.54 ppm (t, J=4.0,
for C H N O Sm (1195.45): C 46.22, H 1.85, N 9.37; found: C
46
22
8
13
2
45.94, H 1.82, N 9.22. For 4: IR (KBr): v˜ =3419, 1618, 1585, 1424,
1
3
.0 Hz, 2H); C NMR (400 MHz, [D ]DMSO): d=169.8, 150.1, 145.2,
1371, 1268, 1228, 1173, 1082, 1007, 923, 854, 790, 733, 706, 657,
6
ꢀ1
40.0, 139.1, 132.4, 127.5, 126.3, 125.2, 124.0, 121.7 ppm; IR (KBr):
628, 551 cm ; elemental analysis calcd (%) for C H N O Eu
46 22 8 13 2
n˜ =3419, 3109, 3075, 2027, 1617, 1540, 1485, 1444, 1397, 1259,
(1198.66): C 45.49, H 1.83, N 9.23; found: C 45.17, H 1.85, N 9.08.
For 7: IR (KBr): v˜ =3512, 3413, 3074,1659, 1594, 1537, 1482, 1449,
1414, 1345, 1270, 1181, 1081, 1022, 924, 865, 796, 734, 702, 661,
ꢀ1
1190, 1112, 1083, 1030, 842, 802, 766, 715, 637, 582, 475 cm ; ele-
mental analysis calcd (%) for C H N O (358.36): C 67.03, H 3.94, N
20
14
4
3
ꢀ
1
1
5.63; found: C 67.26, H 3.92, N 15.45.
635, 576, 462, 425 cm
; elemental analysis calcd (%) for
C H N O Yb (1296.87): C 42.60, H 2.33, N 8.64; found: C 42.92, H
46
30
8
16
2
4
’-(3-pyridylacetonitrile)-2,2’:6’,2“-terpyridine-6,6”-dicarbonitrile:
2
.35, N 8.76.
4
2
’-(3-N-Oxypyridyl)-2,2’:6’,2“-terpyridine-1,1”-di-N-oxide
(0.72 g,
mmol) and Me SiCN (0.891 g, 9 mmol) were added to CH Cl
2
Synthesis of 5 and 6: The procedure is similar to that described
for 2. If NdCl ·6H O in 2 was replaced with TbCl ·6H O and
3
2
(
100 mL). After stirring for 30 min, benzoyl chloride was added
3
2
3
2
over the course of 30 min. After stirring for 48 h at room tempera-
ture, the mixture was evaporated to half its volume. K CO
DyCl ·6H O and the reaction temperature was adjusted to 1808C,
3 2
2
3
two completely different compounds, 5 and 6, were obtained. For
5: IR (KBr): v˜ =3450, 2026, 1620, 1589, 1428, 1374, 1272, 1173,
ꢀ1
(
1
100 mL, 0.8 molL ) was added, and the mixture was stirred for
h. The precipitate was filtered and washed with H O and cold
ꢀ1
2
1010, 851, 792, 708, 628 cm ; elemental analysis calcd (%) for
C H N O Tb (2910.08): C 39.21, H 1.59, N 7.70; found: C 39.34,
CH Cl . The white precipitate was recrystallized with ethanol and
2
2
95 46 16 44
5
DMF, and dried in vacuo to yield a white powder (0.53 g, 68%).
H 1.57, N 7.82. For 6: IR (KBr): v˜ =3450, 2026, 1620, 1589, 1428,
1374, 1272, 1173, 1010, 851, 792, 708, 628 cm ; elemental analysis
1
ꢀ1
M.p. 263–2658C; H NMR (400 MHz, [D ]DMSO): d=9.02 (d, J=
6
8
.0 Hz, 1H), 8.95 (s, 1H), 8.84 (s, 1H), 8.80 (s, 1H), 8.39 (s 1H), 8.33
calcd (%) for C H N O Dy (2927.99): C 38.97, H 1.58, N 7.65;
95
46 16 44
5
(
d, J=8.0 Hz, 1H), 8.24 ppm (d, J=8.0 Hz, 1H); IR (KBr): n˜ =3447,
found: C 38.92, H 1.57, N 7.69.
3
1
072, 2851, 2237, 2025, 1639, 1577, 1539, 1455, 1389, 1274, 1126
080, 988, 904, 858, 819, 739, 635, 575, 468 cm ; elemental analy-
ꢀ
1
sis calcd (%) for C H N (385.39): C 71.68, H 2.88, N 25.44; found:
2
3
11
7
C 71.83, H 2.85, N 25.32.
X-ray crystallography
4
’-(3-carboxylpyridyl)-2,2’:6’,2“-terpyridine-6,6”-dicarboxylic
Single-crystal X-ray diffraction measurements for 1–7 were per-
formed on a Bruker Smart Apex II CCD diffractometer using graph-
ite monochromatic Mo Ka radiation (l=0.71073 ꢁ) at 296 K. The
structures were solved by direct methods and refined by full-
acid: KOH was added as a base to a solution of 4’-(3-pyridylaceto-
nitrile)-2,2’:6’,2“-terpyridine-6,6”-dicarbonitrile (0.39 g, 1 mmol) in
ethanol/H O (v/v, 4:1, 50 mL). The reaction mixture was heated at
reflux for 6 h. Then, the pH was adjusted to three with an aqueous
solution of HCl (1 molL ). The yellow precipitate was filtered, re-
crystallized with ethanol and DMF, and dried in vacuo to yield
2
2
[28]
matrix least-squares on F with the SHELX-97 program.
The
ꢀ1
metal atoms were located from the E-maps, and the other non-hy-
drogen atoms were located in successive difference Fourier synthe-
ses. All non-hydrogen atoms were refined with anisotropic thermal
parameters. The hydrogen atoms on the carbon atoms were posi-
tioned geometrically. The crystallographic data and structural re-
finements for 1–7 are listed in Table 1. Selected bond lengths and
angles for 1–7 are listed in Table S1 in the Supporting Information.
1
a yellow powder (0.36 g, 81%). M.p. 265–2678C; H NMR (400 MHz,
[
D ]DMSO): d=12.85 (s, 1H), 9.12 (s, 2H), 8.88 (m, 4H), 8.58 (m,
6
13
1
H), 8.21 (d, J=32 Hz, 3H), 7.88 ppm (d, J=44 Hz, 1H); C NMR
(
400 MHz, [D ]DMSO): d=171.3, 171.1, 170.9, 160.3, 160.1, 159.6,
6
1
58.9, 155.8, 155.6, 155.4, 154.7, 152.9, 152.0, 151.2, 144.3, 144.1,
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2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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