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over MgSO , filtered, and solvent was then removed under reduced
elemental analysis calcd (%) for C H N O ·0.3H O: C 76.54, H 9.10,
4
35 49
3
2
2
pressure. A crude pale yellow oil was obtained which was purified
using normal phase silica column chromatography (eluting with
N 7.65; found: C 76.01, H 9.17, N 7.44.
III
General synthesis of europium complexes: Eu complexes were
prepared by heating at reflux ligands 1(R) and 1(S) with [Eu(-
CF SO ) ]·6H O or [Eu(ClO ) ] (50 wt.% in H O; 0.33 equiv) in aceto-
9
5% chloroform and 5% methanol (R =0.9)).
f
3
3 3
2
4 4
2
2
6
Synthesis of benzyl (R)-N -hexadecyl-N -(1-(naphthalen-2-yl)eth-
yl) pyridine-2,6-dicarboxamide (1(R)): Compound 1(R) was syn-
nitrile for 30 min at 808C under microwave irradiation. The solution
was subsequently cooled to room temperature and complexes
were precipitated out of the solution as colourless oils. Caution:
Perchlorate salts in presence of organic ligands are potentially explo-
sive and therefore should be handled in small quantities following
adequate precautions.
ꢁ
3
thesized by stirring a solution of 8(R) (0.690 g, 2.16ꢂ10 mol),
ꢁ3
HOBt (0.31 g, 2.29ꢂ10 mol) and hexadecylamine (9, 0.53 g, 2.19ꢂ
ꢁ
3
1
0
mol) in 50 mL of anhydrous THF for 30 min at 08C with
ꢁ
3
a CaCl drying tube before adding EDCI (0.4 mL, 2.3ꢂ10 mol) and
2
ꢁ3
triethylamine (0.45 mL, 3.23ꢂ10 mol) dropwise in 25 mL of dry
THF according to the general procedure. After a further 30 min of
stirring at 08C the solution was allowed to reach room tempera-
ture and left stirring for 48 h. After the work-up described in the
general procedure, the reaction yielded 0.985 g of a light-yellow
crude oil in 84% yield. The crude oil was then purified using
normal phase silica column chromatography using a 95% chloro-
Synthesis of [Eu(1(R)) (CF SO ) ]: The complex was synthesised ac-
3
3
3 3
cording to the general procedure using ligand 1(R) (0.0544 g,
ꢁ4
ꢁ5
1
.00ꢂ10 mol) and [Eu(CF SO ) ]·6H O (0.0200 g, 3.33ꢂ10 mol).
3 3 3 2
A sticky oil was obtained after solvent evaporation (0.0500 g,
1
6
7
6
4
1
1
1
7.3% yield). H NMR (400 MHz, CD CN): d =8.88, 8.75, 8.63, 8.27,
3 H
.59, 7.21, 7.18, 7.08, 7.03, 6.98, 6.91, 6.69, 6.53, 6.50, 6.26, 6.20,
.13, 6.04, 5.86, 5.72, 5.14, 5.08, 4.84, 4.75, 4.68, 4.56, 4.45, 4.23,
.07, 3.97, 3.92, 3.79, 3.46, 3.13, 3.03, 2.74, 2.43, 2.29, 1.94, 1.73,
.54, 1.46, 1.28, 0.88 ppm; IR n˜ max =3476, 3278, 3099, 2924, 1636,
596, 1561, 1511, 1460, 1351, 1284, 1243, 1226, 1197, 1104, 1031,
1
form/5% methanol solvent mixture. H NMR (600 MHz, CDCl ): d =
3
H
8
7
.32 (d, J=8.3 Hz, 1H, NH), 8.30 (d, J=7.7 Hz, 1H, PyH), 8.26 (d, J=
.7 Hz, 1H, PyH), 7.96 (d, J=4.6 Hz, 1H, NH), 7.90 (t, J=7.8 Hz, 1H,
PyH), 7.75 (m, 3H, NaphH), 7.71 (m, 1H, NaphH), 7.48 (d, J=8.6 Hz,
ꢁ1
+
018, 921, 858, 841, 822, 753, 712, 660 cm ; HRMS (MALDI-MS ):
1
3
H, NaphH), 7.42 (m, 2H, NaphH), 5.52 (q, J=7.4 Hz, 1H, NHCH),
.32 (m, 2H, NHCH ), 1.66 (d, J=6.9 Hz, 3H, CHCH ), 1.50 (m, 2H,
+
m/z calcd for C H N O F S Eu: 994.2078 [Eu(1(R))(CF SO ) ] ;
37
49
3
8
6
2
3
3 2
2
3
found: 994.2067 (only 1:1 M/L complex found); elemental analysis
calcd (%) for C108H147EuF N O S : C 58.15, H 6.64, N 5.65; found: C
CH CH ), 1.25 (m, 26H, (CH2)13), 0.88 ppm (t, J=7.0 Hz, 3H,
3
2
1
3
9
9
15 3
CH CH ); C NMR (150 MHz, CDCl ): d =163.35, 162.85, 148.87,
2
3
3
C
5
8.12, H 6.68, N 5.41.
1
1
2
2
1
1
48.66, 140.14, 138.75, 133.17, 132.62, 128.45, 127.69, 127.53,
26.23, 125.94, 124.95, 124.90, 124.72, 124.48, 48.68, 39.54, 31.85,
9.63, 29.61, 29.59, 29.58, 29.56, 29.54, 29.48, 29.29, 29.24, 26.96,
2.62, 21.22, 14.05 ppm; IR n˜ max: 3304, 2923, 2853, 1651, 1522,
466, 1444, 1377, 1338, 1310, 1272, 1237, 1181, 1130, 1105, 1074,
Using the same procedure, [Eu(1(R)) (ClO ) ] was synthesised with
the ClO4 counterion using 1(R) (0.0302 g, 5.52ꢂ10 mol) and
3
4 3
ꢁ
ꢁ5
ꢁ
5
[
7
Eu(ClO ) ] (0.0083 g, 1.84ꢂ10 mol). The oil obtained (0.0300 g,
4 3
+
8.4% yield) was analysed by HRMS. HRMS (MALDI-MS ) m/z calcd
+
ꢁ1
for
437.5796 (only 1:2 M/L complex found).
Synthesis of [Eu(1(S)) (CF SO ) ]: The complex was synthesized ac-
C H N O12Cl Eu: 1437.5832 [Eu(1(R)) (ClO ) ] ; found:
70 98 6 2 2 4 2
000, 953, 891, 855, 845, 817, 746, 675 cm ; elemental analysis
1
calcd (%) for C H N O ·0.3H O: C 76.54, H 9.10, N 7.65; found: C
3
5
49
3
2
2
+
7
6.85,
H
9.05,
N
7.43; HRMS (MALDI-MS ): m/z calcd for
3
3
3 3
+
cording to the general procedure using ligand 1(S) (0.0520 g,
C H N O Na: 566.3722 [M+Na] ; found: 566.3701.
3
5
49
3
2
ꢁ5
ꢁ5
9
.56ꢂ10 mol) and [Eu(CF SO ) ]·6H O (0.0191 g, 3.19ꢂ10 mol).
3 3 3 2
2
6
A sticky oil was obtained after solvent evaporation (0.0465 g,
Synthesis of benzyl (S)-N -hexadecyl-N -(1-(naphthalen-2-yl)eth-
yl) pyridine-2,6-dicarboxamide (1(S)): Compound 1(S) was syn-
1
6
5.4% yield). H NMR (400 MHz, CD CN): d =8.88, 8.75, 8.63, 8.26,
3 H
ꢁ
3
7.96, 7.60, 7.29, 7.21, 7.18, 7.08, 7.03, 6.92, 6.68, 6.53, 6.50, 6.26,
6.19, 6.12, 6.03, 5.86, 5.72, 5.31, 5.12, 4.84, 4.75, 4.68, 4.55, 4.45,
4.23, 4.06, 3.97, 3.93, 3.79, 3.46, 3.14, 3.03, 2.74, 2.44, 2.24, 1.94,
1.28, 0.88, 0.67 ppm; IR n˜ max =3283, 3102, 2926, 2855, 1637, 1596,
1564, 1511, 1460, 1350, 1283, 1243, 1226, 1197, 1170, 1106, 1031,
thesised by stirring a solution of 8(S) (0.484 g, 1.51ꢂ10 mol),
HOBt (0.20 g, 1.5ꢂ10 mol) and hexadecylamine (9, 0.36 g, 1.5ꢂ
mol) in 45 mL of anhydrous THF for 30 min at 08C with
a CaCl drying tube before adding EDCI (0.30 mL, 1.7ꢂ10 mol)
and triethylamine (0.30 mL, 2.1ꢂ10 mol) dropwise in 20 mL of
dry THF, according to the general procedure. After a further 30 min
of stirring at 08C the solution was allowed to reach room tempera-
ture and then it was left stirring for 48 h. After the work-up de-
scribed in general procedure, the reaction yielded 0.692 g of
a light-yellow crude oil in 84% yield. The crude oil was then puri-
fied using normal phase silica column chromatography using 95%
ꢁ3
ꢁ3
1
0
ꢁ3
2
ꢁ3
ꢁ
1
1
018, 859, 842, 821, 750, 661 cm ; elemental analysis calcd (%) for
C108H147EuF N O S : C 58.15, H 6.64, N 5.65; found: C 58.42, H 6.74,
9
9
15 3
+
N 5.74; HRMS (MALDI-MS ): m/z calcd for C H N O F S Eu:
94.2078 [Eu(1(S))(CF SO ) ] ; found: 994.2093 (only 1:1 M/L com-
3 3 2
37 49
3
8 6 2
+
9
plex found).
Using the same procedure, [Eu(1(S))
(ClO
)
] was synthesized with
3
4
3
1
ꢁ
ꢁ5
chloroform/5% methanol solvent mixture. H NMR (600 MHz,
CDCl ): d =8.36 (brm, 1H, NH), 8.30 (d, J=7.7 Hz, 1H, PyH), 8.26
d, J=7.7 Hz, 1H, PyH), 8.00 (brm, 1H, NH), 7.89 (t, J=7.7 Hz, 1H,
PyH), 7.74 (m, 3H, NaphH), 7.70 (m, 1H, NaphH), 7.47 (d, J=8.6 Hz,
the ClO
[Eu(ClO
75.2% yield) was analysed by HRMS (MALDI-MS ): m/z calcd for
4
counterion, using 1(S) (0.0300 g, 5.52ꢂ10 mol) and
) ] (0.0083 g, 1.84ꢂ10 mol). The oil obtained (0.0288 g,
4 3
ꢁ
5
3
H
+
(
+
C H N O12Cl Eu:1437.5832 [Eu(1(S)) (ClO ) ] ; found: 1437.5809
70 98 6 2 2 4 2
1
3
H, NaphH), 7.42 (m, 2H, NaphH), 5.52 (q, J=7.4 Hz, 1H, NHCH),
.30 (m, 2H, NHCH ), 1.65 (d, J=6.9 Hz, 3H, CHCH ), 1.48 (m, 2H,
(only 1:2 M/L complex found).
2
3
CH CH ), 1.25 (m, 26H, (CH2)13), 0.88 ppm (t, J=7.0 Hz, 3H,
3
2
1
3
CH CH ); C NMR (150 MHz, CDCl ): d =163.36, 162.86, 148.85,
2
3
3
C
Acknowledgements
1
1
2
2
1
1
48.65, 140.13, 138.72, 133.14, 132.59, 128.41, 127.67, 127.51,
26.21, 125.92, 124.93, 124.87, 124.72, 124.46, 48.64, 39.53, 31.84,
9.62, 29.60, 29.58, 29.57, 29.56, 29.53, 29.47, 29.28, 29.23, 26.94,
2.60, 21.21, 14.04 ppm; IR n˜ max =3308, 2923, 2853, 1651, 1522,
466, 1444, 1376, 1338, 1309, 1272, 1237, 1181, 1130, 1105, 1074,
We thank Dr. Martin Feeney and Dr. Garry Hessman for the
help with mass spectrometry studies, Dr. John O’Brien and Dr.
Manuel Ruether for the help with NMR studies. We thank Sci-
ence Foundation Ireland for Financial support (SFI PI Awards
10/IN.1/B2999 and 13/IA/1865, to T.G.), the Irish Research
ꢁ1
+
000, 953, 891, 854, 845, 817, 746, 670 cm ; HRMS (MALDI-MS ):
+
m/z calcd for C H N O Na: 566.3722 [M+Na] ; found: 566.3707;
3
5
49
3
2
Chem. Eur. J. 2016, 22, 1 – 16
13
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ