Job/Unit: I42015
/KAP1
Date: 06-05-14 17:44:21
Pages: 11
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FULL PAPER
1
599 (s), 1554 (m), 1504 (w), 1477 (s), 1446 (m), 1394 (m), 1334 (400 MHz, [D
6
]DMSO): δ = 8.43 (d, 4 H, CH=N), 8.40 (s, 2 H,
(m), 1305 (m), 1277 (s), 1246 (m), 1200 (m), 1153 (w), 1126 (w),
PyH), 8.37 (s, 2 H, PyH), 7.25 (s, 2 H, PyH), 7.23 (s, 2 H, PyH),
1
8
090 (w), 1067 (w), 1030 (m), 989 (w), 947 (w), 897 (m), 862 (w),
7.16 (m, 8 H, ArH), 6.62 (d, J = 8 Hz, 4 H, ArH), 6.42 (t, 4 H,
43 (w), 812 (w), 764 (m), 648 (w), 606 (w), 570 (w), 534 (w), 513 ArH), 3.72 (s, 8 H, CH
2
), 3.55 (s, 80 H, COOMe), 2.95 (s, 2 H,
–1
(w), 461 (w) cm . ESI-MS (MeCN): m/z (%) = 1233.70 (100) [M –
CH), 1.82 (s, 54 H, CH
ppm.
2
), 1.32 (m, 4 H, CH ), 0.93 (m, 80 H, CH )
2
3
+
H] .
Complex 4: Yield 0.099 g (54%). C46
calcd. C 45.03, H 3.45, N 10.27; found C 44.95, H 3.57, N 10.24.
IR (KBr): ν˜ = 2916 (w), 2526 (w), 2316 (w), 1649 (vs), 1620 (s),
H
42ErN
9
O
13Zn
2
(1226.91):
Poly(MMA-co-2) (100:1): Yield 74%. IR (KBr): ν˜ = 3624 (w), 3554
(w), 3439 (w), 2997 (s), 2952 (s), 2844 (m), 2362 (w), 2225 (w), 1959
(w), 1729 (vs), 1652 (m), 1601 (w), 1550 (w), 1479 (s), 1448 (s),
1386 (m), 1274 (m), 1244 (m), 1193 (m), 1149 (m), 1062 (m), 1031
(w), 987 (s), 966 (m), 906 (w), 842 (m), 752 (s), 696 (s), 675 (w),
1601 (s), 1550 (m), 1502 (w), 1476 (s), 1445 (m), 1394 (m), 1332
(m), 1304 (m), 1275 (s), 1248 (m), 1200 (m), 1155 (w), 1126 (w),
–
1
1
8
094 (w), 1069 (w), 1032 (m), 989 (w), 947 (w), 897 (m), 866 (w),
41 (w), 812 (w), 766 (m), 648 (w), 608 (w), 569 (w), 534 (w), 511
605 (w), 570 (w), 484 (w), 414 (w) cm .
Poly(MMA-co-3): Yield 70 (50:1), 75 (100:1), 87% (200:1). IR
–1
(w), 461 (w) cm . ESI-MS (MeCN): m/z (%) = 1227.92 (100) [M –
(
(
KBr): ν˜ = 3628 (w), 3551 (w), 3437 (w), 2997 (s), 2952 (s), 2849
m), 2362 (w), 2227 (w), 2048 (w), 1959 (w), 1730 (vs), 1656 (m),
+
H] .
Complex 5: Yield 0.089 g (49%). C46
calcd. C 45.40, H 3.48, N 10.36; found C 45.51, H 3.53, N 10.30.
IR (KBr): ν˜ = 2909 (w), 2480 (w), 2320 (w), 1645 (vs), 1616 (s),
H
42GdN
9
O
13Zn
2
(1216.90):
1602 (w), 1550 (w), 1483 (s), 1450 (vs), 1386 (m), 1272 (m), 1244
(m), 1193 (m), 1149 (m), 1062 (m), 1031 (w), 987 (s), 966 (m), 906
(w), 842 (m), 752 (s), 698 (s), 673 (w), 603 (w), 572 (w), 486 (w),
–
1
1599 (s), 1553 (m), 1504 (w), 1474 (s), 1446 (m), 1391 (m), 1339
420 (w) cm .
(
1
8
m), 1302 (m), 1277 (s), 1248 (m), 1199 (m), 1157 (w), 1126 (w),
Poly(MMA-co-4) (100:1): Yield 73%. IR (KBr): ν˜ = 3620 (w), 3548
087 (w), 1070 (w), 1030 (m), 989 (w), 947 (w), 897 (m), 860 (w),
43 (w), 812 (w), 762 (m), 648 (w), 607 (w), 571 (w), 534 (w), 507
(
(
w), 3438 (w), 2997 (s), 2951 (s), 2852 (m), 2362 (w), 2227 (w), 2048
w), 1959 (w), 1730 (vs), 1652 (m), 1604 (w), 1550 (w), 1481 (s),
–1
(w), 457 (w) cm . ESI-MS (MeCN): m/z (%) = 1217.91 (100) [M –
1448 (s), 1386 (s), 1274 (m), 1242 (m), 1193 (m), 1149 (m), 1062
+
H] .
(
m), 1031 (w), 987 (s), 966 (m), 902 (w), 842 (m), 750 (s), 696 (s),
–
1
PMMA Activated with AIBN: The homogeneous polymerization of
MMA activated with AIBN for comparison was performed in a
Fisher–Porter glass reactor and protected by nitrogen according to
the typical procedure. To a solution of MMA (2 mL, 19 mmol)
in dry xylene (20 mL), AIBN initiator (28.2 mg, 1.5 mol-% of
MMA) was added, and the resultant homogeneous solution was
682 (w), 607 (w), 570 (w), 484 (w), 416 (w) cm .
Poly(MMA-co-5) (100:1): Yield 72%. 3626 (w), 3548 (w), 3437 (w),
2
1
1
995 (s), 2951 (s), 2851 (m), 2360 (w), 2229 (w), 2048 (w), 1959 (w),
730 (vs), 1654 (m), 1602 (w), 1550 (w), 1479 (s), 1446 (s), 1384 (s),
278 (m), 1245 (m), 1193 (m), 1149 (m), 1062 (m), 1031 (w), 987
[
31]
(
5
s), 966 (m), 910 (w), 842 (m), 750 (s), 698 (s), 678 (w), 607 (w),
72 (w), 486 (w), 418 (w).
2 2
purged with N for 10 min and sealed under a reduced N atmo-
sphere. The mixture was heated to 80 °C with continuous stirring
for 16 h. The viscous mixture was diluted with dry THF (20 mL)
and precipitated with absolute diethyl ether (100 mL) three times.
The resulting solid PMMA product was collected by filtration and
dried at 45 °C under vacuum to constant weight.
X-ray Crystallography: Single crystals of 1 of suitable dimensions
were mounted onto thin glass fibers. The intensity data were col-
lected with a Bruker SMART CCD diffractometer (Mo-K radia-
α
tion and λ = 0.71073 Å) in Φ and ω scan modes. The structure was
solved by direct methods followed by difference Fourier syntheses
PMMA: Yield 93%. IR (KBr): ν˜ = 3082 (w), 3061 (w), 3026 (w),
2
(
1
2
and then refined by full-matrix least-squares techniques against F
by using SHELXL-97.
994 (s), 2951 (s), 1944 (w), 1872 (w), 1803 (w), 1728 (vs), 1601
[36]
All non-hydrogen atoms were refined
m), 1545 (w), 1493 (m), 1452 (m), 1381 (s), 1180 (w), 1069 (w),
with anisotropic thermal parameters. Absorption correction was
–
1 1
028 (w), 998 (s), 841 (w), 758 (m), 698 (m), 540 (w) cm .
]DMSO): δ = 3.57 (s, 3 H, COOCH ), 1.84
), 0.95 (m, 3 H, CH ) ppm.
H
[37]
applied by using SADABS. Hydrogen atoms were placed in cal-
NMR (400 MHz, [D
b, 2 H, CH
6
3
culated positions and refined isotropically by using a riding model.
(
2
3
CCDC-982613 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
PMMA-supported Metallopolymers Poly{MMA-co-[Zn
vp) Ln(NO ]}: A mixture of MMA (1 mL, 9.5 mmol), [Zn
vp) Ln(NO
2
(L)
2
(4-
(4-
2
3
)
3
2
(L)
2
2
3
)
3
] (0.095 mmol, 114 mg, Ln = La, Nd, and Yb;
1
1
17 mg, Ln = Er; 116 mg, Ln = Gd), and AIBN initiator (14.1 mg,
.5 mol-% of the monomer MMA) was dissolved in dry xylene
Supporting Information (see footnote on the first page of this arti-
cle): Selected bond lengths [Å] and angles [°] for 1, visible emission
(15 mL), and the resultant homogeneous solution was purged with
2
and excitation spectra of H L, the precursor, and 5 in absolute
N
2
for 10 min and sealed under a reduced N atmosphere. The
2
–
5
MeCN solution at 1ϫ10 m, and visible emission and excitation
spectra of poly(MMA-co-5) with a monomer feed molar ratio of
mixture was heated to 80 °C with continuous stirring for 16 h. The
viscous mixture was diluted with dry THF (15 mL) and precipi-
tated with absolute diethyl ether (50 mL) three times. The resulting
100:1 in the solid state at room temperature.
2 2 2 3 3
solid poly{MMA-co-[Zn (L) (4-vp) Ln(NO ) ]} products were col-
lected by filtration and dried at 45 °C under vacuum to constant
weight.
Acknowledgments
Poly(MMA-co-1) (100:1): Yield 77%. IR (KBr): ν˜ = 3626 (w), 3548 This work is funded by the National Natural Science Foundation
(
(
1
(
6
w), 3437 (w), 2997 (s), 2951 (s), 2853 (m), 2362 (w), 2231 (w), 2048
w), 1959 (w), 1728 (vs), 1654 (m), 1602 (w), 1550 (w), 1483 (m), 20871098), the Ministry of Education of China (Program for New
450 (m), 1386 (s), 1272 (m), 1242 (m), 1193 (m), 1149 (m), 1062 Century Excellent Talents in University, NCET-10-0936), the Re-
m), 1033 (w), 989 (s), 966 (m), 910 (w), 842 (m), 750 (s), 696 (s), search Fund for the Doctoral Program of Higher Education
of China (NSFC) (grant numbers 21373160, 91222201, 21173165,
–1
1
73 (w), 605 (w), 570 (w), 484 (w), 416 (w) cm . H NMR (20116101110003), the Education Committee Foundation
Eur. J. Inorg. Chem. 0000, 0–0
9
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