FULL PAPER
+ Na]+, 1554.0 [2M + Na]+, found 788.9 [M + Na]+, 1554.3 [2M
+ Na]+.
ICP-OES measurements were performed by Ms. Elvira Vassilieva
(Department of Earth and Environmental Sciences). Mr. Karel
Duerinckx is acknowledged for his help with the NMR spec-
troscopy measurements. S. L., L. V. E. and R. N. M. thank the
ARC Programs of the French Community of Belgium, the Fonds
National de la Recherche Scientifique (FNRS), the support and
sponsorship provided by COST Actions (D38 and TD1004) and
the EMIL program.
157GdIII–DTPA–BNaphA Gd3: Yield: 66%. IR: νmax = 1593 (COO–
˜
asym. stretch), 1512 (amide II), 1398 (COO– sym. stretch) cm–1.
ESI-MS (+ mode): m/z: calcd. 849.0 [M
+
Na]+, 1675.0
[2M + Na]+, found 849.3 [M + Na]+, 1676.7 [2M + Na]+. UV/Vis:
λ (ε, m–1 cm–1) = 219 (87800), 272 (9050), 282 (10550), 291 (7500)
nm. 152EuIII–DTPA–BNaphA: Yield: 76%. IR: νmax = 1589 (COO–
˜
asym. stretch), 1510 (amide II), 1400 (COO– sym. stretch) cm–1.
ESI-MS (+ mode): m/z: calcd. 843.7 [M
+
Na]+, 1664.4
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nm. TbIII–DTPA–BNaphA: Yield: 67%. IR: ν
= 1591 (COO–
˜
max
asym. stretch), 1514 (amide II), 1398 (COO– sym. stretch) cm–1.
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+
Na]+, 1678.2
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nm. YIII–DTPA–BNaphA: Yield: 80%. 1H NMR (300 MHz,
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–
CD3OD, 25 °C, SiMe4): δ = 1.87 (t, 4 H, CH2–CH2–N–CH2–CO2 ),
–
2.09 (t, 4 H, CH2–CH2–N–CH2–CO2 ), 2.49 (s, 2 H, N–CH2–
–
–
CO2 ), 2.91 (s, 4 H, N–CH2–CO–NH), 2.98 (s, 4 H, N–CH2–CO2 ),
4.63 (s, 4 H, CH2–naphthyl), 7.29, 7.40 (m, 4 H, naphthyl CH),
7.64, 7.71, 7.83 (d, 2 H, naphthyl CH) ppm. IR: νmax = 1593 (COO–
˜
asym. stretch), 1512 (amide II), 1402 (COO– sym. stretch) cm–1.
ESI-MS (+ mode): m/z: calcd. 780.6 [M
+
Na]+, 1538.2
[2M + Na]+, found 781.9 [M + Na]+, 1538.7 [2M + Na]+.
157GdIII–DTPA–BEthA Gd4: Yield: 50%. IR: ν = 1583 (COO–
˜
max
asym. stretch), 1508 (amide II), 1396 (COO– sym. stretch) cm–1.
ESI-MS (+ mode): m/z: calcd. 768.8 [M
+
Na]+, 1514.6
[2M + Na]+, found 769.1 [M + Na]+, 1515.0 [2M + Na]+. UV/Vis:
λ (ε, m–1 cm–1) = 263 (35380) nm. 152EuIII–DTPA–BEthA: Yield:
59%. IR: νmax = 1585 (COO– asym. stretch), 1509 (amide II), 1395
˜
(COO– sym. stretch) cm–1. ESI-MS (+ mode): m/z: calcd. 763.6 [M
+ Na]+, 1504.2 [2M + Na]+, found 763.9 [M + Na]+. UV/Vis: λ (ε,
m
–1 cm–1) = 263 (36100) nm. TbIII–DTPA–BEthA: Yield: 42%. IR:
ν
= 1583 (COO– asym. stretch), 1508 (amide II), 1394 (COO–
˜
max
sym. stretch) cm–1. ESI-MS (+ve mode): m/z: calcd. 770.5 [M +
Na]+, 1518.0 [2M + Na]+, found 770.9 [M + Na]+, 1517.8 [2M +
Na]+. UV/Vis: λ (ε, m–1 cm–1) = 263 (37150) nm. YIII–DTPA–
BEthA: Yield: 29%. IR: ν
= 1590 (COO– asym. stretch), 1510
˜
max
(amide II), 1398 (COO– sym. stretch) cm–1. ESI-MS (+ mode): m/z:
calcd. 700.5 [M
Na]+, 1378 [2M Na]+, found 699.7
[M + Na]+, 1377.6 [2M + Na]+.
+
+
Supporting Information (see footnote on the first page of this arti-
cle): 1H NMR spectra of ligands 1–4 (Figure S1), 1H NMR spectra
of DTPA–BCoumA and DTPA–BNaphA compared to their YIII
complexes (Figure S2), ESI mass spectra of the 152EuIII complexes
(Figure S3), UV/Vis absorption spectra of EuIII and TbIII com-
plexes (Figure S4), relative integral intensities of f–f transitions for
EuIII complexes (Table S1) and TbIII complexes (Table S2).
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Acknowledgments
[7] a) G. Dehaen, P. Verwilst, S. V. Eliseeva, S. Laurent, L.
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E. D. and T. N. P. V. acknowledge the IWT Flanders (Belgium) and
the FWO Flanders (project number G.0412.09) for financial sup-
port. S. V. E. was a visiting postdoctoral fellow of the FWO Flan-
ders (project number G.0412.09) and now works at the Centre de
Biophysique Moléculaire - CNRS in Orléans. S. V. E and S. P.
thank La Ligue contre le Cancer and the French National Research
Agency (ANR) (project number ANR-10-BLAN-1513). CHN mi-
croanalysis was performed by Mr. Dirk Henot. ESI-MS measure-
ments were done by Mr. Dirk Henot and Mr. Bert Demarsin and
Eur. J. Inorg. Chem. 2013, 2629–2639
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