Sensitizers of Lanthanide Luminescence via Low-Energy Excitation
3
3
4.43 (s, 3 H, NCH3), 4.43 (m, 2 H, H1), 7.29 (ddd, J = 7.8, J =
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4
4
7.3, J = 1.8 Hz, 1 H, HPh), 7.67 (d, J = 2.5 Hz, 1 H, HPy), 7.79
(dd, 3J = 8.7, 4J = 1.8 Hz, 1 H, HPh), 7.81 (dd, 3J = 8.7, 3J =
[2]
[3]
[4]
4
7.8 Hz, 1 H, HPh), 7.88 (s, 1 H, HBenz.), 8.06 (d, J = 2.5 Hz, 1 H,
H
Py), 8.35 (d, 3J = 7.3 Hz, 1 H, HPh), 8.66 (s, 1 H, HBenz.) ppm.
13C NMR (150.864 MHz, [D6]DMSO): δ = 33.14 (NCH3), 34.52
(NCH3), 58.06 (OCH3), 68.22 (OCH2), 68.57 (OCH2), 69.54
(OCH2), 69.82 (OCH2), 70.05 (OCH2), 71.29 (OCH2), 95.71
(CHBenz.), 112.43 (CHPy), 112.61 (CHPy), 115.73 (CHPh), 117.06
(CBenz. quat.), 119.25 (CHPh), 120.27 (CHBenz.), 120.47 (CPh quat.),
126.68 (CBenz.Ph), 133.92 (CHPh), 137.36 (CBenz. quat.), 139.83
(CHPh), 142.26 (CPh quat.), 142.56 (CBenz. quat.), 149.50 (CBenz. quat.),
150.98 (CPy quat.), 151.88 (CPy quat.), 165.71 (CPy-O quat.), 166.10
(COOH), 177.11 (C=O) ppm. ESI-MS m/z calcd. for [M + H+]
(found): 547.22 (547.08), for [2M+H+] (found): 1093.43 (1093.45).
C29H30N4O7 (546.58): calcd. C 63.73, H 5.53, N 10.25; found C
63.25, H 5.53, N 10.13.
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
Synthesis of the LnIII Complexes (General Procedure): The HLABX
ligand was suspended in a ethanol/H2O (5:5 mL) mixture followed
by the addition of 1 mL of aqueous sodium hydroxide and sub-
sequently stirred at room temperature for 15 min. to give a yellow
solution. The solution was warmed up to 70–80 °C and
LnCl3·6H2O in 1 mL of distilled water was added dropwise over
10 min. A yellow precipitate was formed and the resulting suspen-
sion was stirred for 30 min. After cooling, the precipitate was fil-
tered, washed with distilled water (ca. 20 mL) and ethyl ether (ca.
20 mL). The precipitate so collected was then re-dissolved in
CH2Cl2/MeOH (18:2 mL) or CHCl3 (20 mL). The organic solution
was concentrated under reduced pressure and subsequently dried
under vacuum at room temperature to give colored solids.
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[Eu(LAB1)3]: The reaction was performed with HLAB1 (30 mg,
54.9 µmol), NaOH (2.56 mg, 0.641 mmol) and EuCl3·6H2O
(6.71 mg, 0.183 mmol). Yellow-orange solid: 29.2 mg (88% yield).
C87H87EuN12O21·2H2O (1824.72): calcd. C 57.26, H 5.03, N 8.66;
found C 57.22, H 5.19, N 9.21.
[Yb(LAB2)3]: The reaction was performed with HLAB2 (40 mg,
0.732 mmol), NaOH (2.93 mg, 0.732 mmol) and YbCl3·6H2O
(9.46 mg, 0.244 mmol). Brown-orange solid: 43.3 mg (98% yield).
C87H87N12O21Yb·H2O (1827.77): calcd. C 57.17, H 4.91, N 9.20;
found C 57.43, H 5.20, N 9.29.
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Supporting Information (see also the footnote on the first page of
this article): Syntheses of all intermediates; data of ESI-TOF mass
spectra for lanthanide complexes (Tables S1, S2); absorption spec-
tra, distribution diagrams and recalculated absorption spectra for
spectrophotometric titrations of ligands (LABX)– by lanthanide per-
chlorates (Figures S1–S9); absorption spectra of ligand (LAB2)– and
its complexes (Figure S10) and luminescence spectra of ligands
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
(LABX –
) and some of their complexes in neat MeCN at both 77
(with a 50 µs time delay) and 295 K (Figures S11, S12)
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Acknowledgments
This research is supported by the Swiss National Science Founda-
tion (grant 200020_119866). J. C. B. thanks the World Class Uni-
versity (WCU) program of the National Science Foundation of Ko-
rea (Ministry of Education, Science, and Technology) for a grant
(R31-10035).
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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