Luminescent Lanthanide Complexes
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elemental analysis calcd (%) for C26H25N8Na5O11.5H2O: C 37.60, H 4.25,
N 13.49; found: C 37.43, H 3.96, N 13.24.
139.0, 145.8, 146.7, 152.0, 166.9, 179.2, 183.0 ppm; IR (ATR): n˜ =3390 (s),
1604 (s), 1580 (s), 1555 (w), 1439 (s), 1406 (s), 1328 (w), 1198 (w), 1129
(w), 1069 cmꢀ1 (w); MS (ESI, MeOH/H2O, negative mode): m/z (%):
397.2 (75) [Mꢀ2Na+]2ꢀ, 257.1 (35) [Mꢀ3Na+]3ꢀ; elemental analysis calcd
(%) for C34H29N8Na5O11.5H2O: C 43.88, H 4.22, N 12.04; found: C 43.54,
H 3.88, N 11.71.
Synthesis of compound 17: In
(100 mg, 0.11 mmol), 6-heptinoic acid (17 mL; 0.13 mmol), [Pd-
(PPh3)2 L2] (8.40 mg; 0.01 mmol), anhydrous THF (10 mL) and freshly
a Schlenk tube were dissolved 3bBu
ACHTUNGTRENNUNG
distilled Et3N (6 mL). The reaction mixture was degassed for 15 min and
CuI (3.4 mg; 0.02 mmol) was added. Reaction was heated at 408C for
72 h. The solvent was evaporated to dryness and the residue was dis-
solved in CH2Cl2 (50 mL). The organic phase was washed with water (2ꢇ
50 mL), dried over Na2SO4 and evaporated to dryness. Flash chromatog-
raphy over silica gel (CH2Cl2/MeOH=100:00 to 95:5) afforded com-
pound 17 (41 mg, 40%) as a colourless oil. 1H NMR (200 MHz, CDCl3):
d=8.65 (d, J=8.8 Hz, 2H), 8.16 (d, J=7.7 Hz, 2H), 7.82 (s, 2H), 7.47–
7.26 (m, 4H), 4.41 (s, 4H), 3.56 (s, 8H), 2.54–2.42 (m, 4H), 1.87–1.71 (m,
4H), 1.48 ppm (s, 36H); 13C {1H} NMR (50 MHz, CDCl3): d=19.3, 24.5,
27.9, 28.3, 45.0, 50.1, 55.7, 79.3, 81.2, 95.7, 112.3, 114.7, 121.7, 122.5, 125.7,
Synthesis of compound 19: 3aBu (480 mg, 0.61 mmol) and ethyl 4-amino-
butyrate hydrochloride salt (204 mg, 1.22 mmol) were dissolved in dis-
tilled toluene (10 mL) and triethylamine (10 mL). [PdACHTUNGTRNEG(UN PPh3)2Cl2] (86 mg,
0.061 mmol) was added. The solution was heated at 1008C under CO at-
mosphere during 24 h. The solution was filtered over celite and the sol-
vents were evaporated to dryness to give a pale yellow oil. The oil was
dissolved in CH2Cl2 (30 mL) and washed with water (3ꢇ15 mL). The or-
ganic phase was dried over Na2SO4, filtered and evaporated under re-
duced pressure. 33 (288 mg, 54%) was isolated as a colourless oil by flash
1
chromatography on silica gel (CH2Cl2/MeOH=100:0 to 99.5:5). H NMR
˜
128.1, 136.4, 139.8, 146.4, 152.3, 170.5, 175.2 ppm; IR (ATR): n=3329
(300 MHz, CDCl3): d=8.43 (d, J=2.2 Hz, 2H), 8.1 (s, 2H), 6.53 (d, J=
2.2 Hz, 2H), 4.06 (q, J=7.0 Hz, 2H), 3.99 (s, 4H), 3.52 (q, J=6.3 Hz,
2H), 3.47 (s, 8H), 2.42 (t, J=7.2 Hz, 2H), 1.97 (qt, J=7.1 Hz, 2H), 1.44
(s, 36H), 1.19 ppm (t, J=6.8 Hz, 3H); 13C {1H} NMR (75 MHz, CDCl3):
d=14.3, 24.5, 28.2, 31.7, 39.8, 51.3, 55.4, 60.5, 81.1, 106.8, 108.8, 128.0,
(br), 3125 (w), 2988 (w), 2929 (w), 2110 (w; nCꢂC), 1734 (s), 1658 (m),
1608 (m), 1581 (s), 1558 (w), 1435 (s), 1403 (s), 1332 (w), 1192 (w), 1133
(w), 1070 cmꢀ1 (w); MS (EI): m/z (%): 949.2 (100) [M]+, 950.2 (30 [M]+;
elemental analysis calcd (%) for C52H67N7O10: C 65.73, H 7.11, N 10.32;
found: C 65.88, H 7.19, N 10.43.
˜
147.7, 150.7, 153.8, 164.9, 170.5, 173.5, 173.7 ppm; IR (ATR): n=3330
Synthesis of ligand L9: 17 (40 mg, 42 mmol) was dissolved in CH2Cl2
(3 mL) and TFA (1.5 mL). The reaction mixture was stirred for 4 h at RT
and evaporated to dryness. The residue was dissolved in MeOH
(0.5 mL), and L9 (20.8 mg, 52%) was precipitated by addition of diethyl
(br), 2978 (w), 2930 (w), 2851 (w), 1731 (m), 1659 (m), 1618 (m), 1570
(m), 1535 (m), 1463 (m), 1391 (m), 1368 (m), 1312 (w), 1282 (w), 1552
(w), 1217 (m), 1142 (s), 1045 (m), 978 (m), 912 cmꢀ1 (m); MS (FAB): m/z
(%): 883.3 (100) [M+H]+; elemental analysis calcd (%) for C44H66N8O11:
C 59.85, H 7.53, N 12.69; found: C 59.67, H 7.33, N 12.53.
ether and isolated as
a
pale brown powder. 1H NMR (200 MHz,
CD3OD): d=8.47 (d, J=8.5 Hz, 2H), 8.17 (s, 2H), 7.83 (d, J=8.5 Hz,
2H), 7.42–7.24 (m, 4H), 4.06 (s, 4H), 3.26 (s, 8H), 2.47–2.30 (m, 4H),
1.77–1.61 ppm (m, 4H); 13C {1H} NMR (50 MHz, CD3OD,): d=25.5, 29.0,
29.5, 34.5, 47.9, 55.5, 79.5, 98.0, 114.0, 115.9, 121.6, 124.9, 126.8, 130.0,
138.2, 140.8, 141.3, 153.1, 170.0, 177.5 ppm; IR (ATR): n˜ =3390 (s), 1604
(s), 1580 (s), 1555 (w), 1439 (s), 1406 (s), 1328 (w), 1198 (w), 1129 (w),
1069 cmꢀ1 (w); MS (ESI, Acetone/H2O): m/z (%): 726.3 (100) [M+H]+;
elemental analysis calcd (%) for C36H35N7O10.H2O: C 58.14, H 5.01, N
13.18; found: C 57.97, H 4.76, N 12.92.
Synthesis of compound 20: 19 (96 mg, 0.11 mmol) was dissolved in THF
(10 mL) and 1 mL of aqueous solution of NaOH (10 mg, 0.24 mmol) was
added. The solution was stirred at 608C during 3 h. The solvents were
distilled off and the residue was dissolved in CH2Cl2 (10 mL), and
washed with an NH4Cl saturated solution in water (3ꢇ5 mL). The aque-
ous phase was washed with CH2Cl2 (3ꢇ10 mL). The combined organic
phases were evaporated to dryness to afford a white solid mixed with col-
ourless oil. The residue was purified by flash chromatography over silica
gel (CH2Cl2/MeOH=100:00 to 98:2) to afford 20 (65 mg, 70%) as a
white solid after drying under reduced pressure. 1H NMR (300 MHz,
CDCl3): d=8.47 (d, J=2.5 Hz, 2H), 8.22 (s, 2H), 6.53 (d, J=2.5 Hz,
2H), 4.01 (s, 4H), 3.54 (m, 2H), 3.50 (s, 8H), 2.54 (t, J=6.0 Hz, 2H),
2.00 (qt, J=6.0 Hz, 2H), 1.46 ppm (s, 36H); 13C {1H} NMR (75 MHz,
CDCl3): d=28.3, 33.3, 40.1, 51.5, 55.8, 81.5, 107.3, 108.9, 128.3, 147.9,
150.6, 153.7, 164.4, 170.8, 178.3 ppm; IR (ATR): n˜ =3330 (w), 2979 (w),
2931 (w), 2850 (w), 1731 (s), 1659 (m), 1618 (m), 1570 (s), 1535 (m),
1463 (s), 1391 (s), 1311 (w), 1252 (m), 1216 (s), 1142 (s), 1045 (m),
978 cmꢀ1 (m); MS (ESI, CH3CN/H2O/TFA 1%): m/z (%): 853.3 (100)
[MꢀNH4+]ꢀ; elemental analysis calcd (%) for C42H61N8O11.NH4.3H2O: C
55.56, H 7.44, N 12.34; found: C 54.47, H 7.73, N 12.69.
Synthesis of compound 18: 3bEt (90 mg, 0.11 mmol) and ethyl 4-aminobu-
tyrate hydrochloride (38 mg, 0.23 mmol) were dissolved in distilled tolu-
ene (10 mL) and triethylamine (10 mL). [PdACTHNUGRTENUNG(PPh3)2 L2] (8 mg,
0.011 mmol) was added and the solution was heated at 1008C under a
continuous flow of CO for 24 h. The solution was filtered over celite and
the solvents were evaporated to dryness to give a pale yellow oil. The oil
was dissolved in CH2Cl2 (30 mL) and washed with water (3ꢇ15 mL). The
organic phase was dried over Na2SO4, filtered and evaporated under re-
duced pressure. 18 (98 mg, 54%) was isolated by flash chromatography
on silica gel (CH2Cl2/MeOH=100:0 to 99.4:0.6) as yellowish oil.
1H NMR (300 MHz, CDCl3): d=8.64 (d, J=8.5 Hz, 2H), 8.17 (d, J=
8.1 Hz, 2H), 8.15 (s, 2H), 7.50–7.28 (m, 4H), 7.18 (t, J=5.4 Hz, 1H), 4.41
(s, 4H), 4.18 (q, J=7.2 Hz, 10H), 3.68 (s, 8H), 3.62–3.55 (m, 2H), 2.47 (t,
J=7.2 Hz, 2H), 2.03 (qt, J=7.2 Hz, 2H), 1.26 ppm (t, J=7.2 Hz, 15H);
13C {1H} NMR (300 MHz, CDCl3): d=14.1, 24.5, 31.9, 39.8, 50.6, 54.8,
60.6, 107.6, 114.5, 121.6, 122.7, 125.6, 128.3, 139.7, 146.5, 146.7, 152.8,
Synthesis of compound 21: In a Schlenk tube under argon, 20 (85 mg,
0.097 mmol) was dissolved in anhydrous CH2Cl2 (10 mL). Disuccinimidyl-
carbonyl (30 mg, 0.12 mmol) and DIEA (34 mL, 0.195 mmol) were added.
The reaction mixture was stirred at RT during 4 h and 10 mL of CH2Cl2
were added. The organic phase was washed with water (2ꢇ10 mL),
HCl 1N (2ꢇ10 mL) and brine (2ꢇ10 mL). The combined organic phase
were dried over Na2SO4 and concentrated to dryness. Flash chromatogra-
phy over silica gel (CH2Cl2/MeOH=100:00 to 95:5) afforded pure 21
(47.7 mg, 52%) as a white solid. 1H NMR(300 MHz, CDCl3): d=8.47 (d,
J=2.6 Hz, 2H), 8.12 (s, 2H), 6.57 (d, J=2.6 Hz, 2H), 4.04 (s, 4H), 3.61
(q, J=6.4 Hz, 2H), 3.51 (s, 8H), 2.85 (s, 4H), 2.75 (t, J=7.2 Hz, 2H),
2.15 (qt, J=7.2 Hz, 2H), 1.46 ppm (s, 36H); 13C NMR (300 MHz,
CDCl3): d=24.4, 25.6, 28.2, 28.5, 38.9, 51.2, 55.3, 81.1, 106.7, 108.8, 128.0,
˜
165.2, 171.1, 173.5 ppm; IR (ATR): n=3329 (br), 3127 (w), 2985 (w),
2934 (w), 1732 (s), 1669 (m), 1613 (m), 1571 (m), 1533 (m), 1466 (s), 1389
(s), 1302 (w), 1261 (w), 1187 (s), 1156 (s), 1092 (w), 1030 cmꢀ1 (s); MS
(EI): m/z (%): 871.2 (100) [M+H]+; elemental analysis calcd (%) for
C44H54N8O11: C 60.68, H 6.25, N 12.87; found: C 60.55, H 6.78, N 14.64.
Synthesis of ligand L10: Compound 18 (50 mg, 57 mmol) was dissolved in
20 mL of MeOH/water=1:1 and NaOH (14 mg, 0.34 mmol) was added.
The reaction mixture was heated at 608C for 4 h. The solvent were
evaporated and the residue was dissolved in water (20 mL). The aqueous
phase was washed with CH2Cl2 (3ꢇ10 mL) and evaporated to afford a
pale yellow residue. The residue was dissolved in water (0.5 mL) and L10
(24 mg, 50%) was obtained as a fine pale brown powder by precipitation
with MeOH, THF and diethyl ether. 1H NMR (300 MHz, D2O): d=8.35
(s, 2H), 7.95 (s, 2H), 7.80 (s, 2H), 7.50–7.36 (m, 4H), 4.08 (s, 4H), 3.27
(m, 10H), 2.30 (m, 2H), 1.88 ppm (m, 2H); 13C NMR (200 MHz, D2O):
d=25.7, 35.3, 40.4, 49.3, 58.7, 107.7, 114.4, 121.5, 123.4, 125.7, 129.0,
˜
147.2, 150.7, 153.7, 165.0, 168.2, 169.2, 170.4 ppm. IR (ATR): n=2979
(w), 2926 (w), 2851 (w), 1812 (w), 1785 (w), 1733 (s), 1666 (w), 1618 (w),
1570 (m) 1534 (m), 1462 (m), 1391 (m), 1367 (m), 1310 (w), 1284 (w),
1249 (w), 1208 (s), 1141 (s), 1067 (m), 1045 (m), 978 cmꢀ1 (m); MS (EI):
m/z (%): 952.3 (100) [M]+; elemental analysis calcd for
C46H65N9O13.H2O: C 56.95, H 6.95, N 12.99; found: C 56.68, H 6.53, N
12.67.
Chem. Eur. J. 2011, 17, 9164 – 9179
ꢅ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9177