Y. Hasegawa et al.
(91%); 1H NMR (300 MHz, CDCl3, 258C): d=7.82–7.84 (d, J=6 Hz,
2H; Ar), 7.53–7.60 (m, 2H; Ar), 7.40–7.46 (m, 2H; Ar), 1.67 (s, 6H;
2Me), 1.35–1.46 ppm (m, 36H; 4tBu); 31P NMR (200 MHz, CDCl3,
258C): d=69.53 (1P), 58.36 (1P) ppm; IR (ATR): n˜ =1180 (st, P=O),
1103–1200 cmꢀ1 (st, C-O-C); FAB-MS: m/z: 531 [M+H]+.
plexes with trigonal dodecahedron structures for the first
time. Such strongly luminescent lanthanide complexes with
distorted coordination structures would open up new fields
in photophysical, coordination, and material chemistry.
Preparation of dpepo: Bis[(2-diphenylphosphino)phenyl] ether (5.0 g,
9.3 mmol) was dissolved in dichloromethane (100 mL) in a 300 mL flask.
The solution was cooled to 08C, and then a 30% H2O2 aqueous solution
(21 mL, 186 mmol) was added. The reaction mixture was stirred at 08C
for 4 h and was then washed with water and extracted three times with
dichloromethane. The organic layer was dried over anhydrous magnesi-
um sulfate and concentrated to dryness. Reprecipitation from hexane
Experimental Section
Materials: Europium acetate monohydrate (99.9%), samarium acetate
tetrahydrate (99.9%), [D6]acetone (D, 99.9%), and CDCl3 (D, 99.8%)
were purchased from Wako Pure Chemical Industries Ltd. 1,1,1,5,5,5-
Hexafluoro-2,4-pentanedione, 4,5-bis(diphenylphosphino)-9,9-dimethyl-
1
gave a white powder of the title compound. Yield: 5.0 g (94%); H NMR
(300 MHz, CDCl3, 258C): d=7.06–7.71 (m, 26H; Ar), 6.02–6.07 ppm (m,
2H; Ar); 31P NMR (200 MHz, CDCl3, 258C): d=26.41 (2P) ppm; IR
(ATR): n˜ =1183 (st, P=O), 1070–1226 cmꢀ1 (st, C-O-C); FAB-MS: m/z:
571 [M+H]+.
General procedure for the preparation of EuIII and SmIII complexes:
Phosphane oxide ligand (1 equiv) and [LnACHTUNTGRNNEUG(hfa)3ACHTUNTGREN(NGUN H2O)2] (1.2 equiv) were
xanthene,
4,5-bis(di-tert-butylphosphino)-9,9-dimethylxanthene,
and
bis[(2-diphenylphosphino)phenyl] ether were obtained from Tokyo Kasei
Organic Chemicals and Aldrich Chemical Company Inc. All other chemi-
cals and solvents were reagent grade and were used without further pu-
rification.
Apparatus: Infrared spectra were recorded using a JASCO FT/IR-420
spectrometer. 1H (300 and 500 MHz) and 31P NMR (200 MHz) spectra
were recorded using a JEOL ECP-500. Chemical shifts are reported in d
(ppm) and are referenced to an internal tetramethylsilane standard for
1H NMR spectroscopy and an external 85% H3PO4 standard for
31P NMR spectroscopy. Mass spectra were measured using a JEOL JMS-
700M Station. Elemental analyses were performed using a Perkin–Elmer
2400II instrument.
dissolved in methanol (30 mL). The solution was heated at reflux while
stirring for 8 h, and the reaction mixture was concentrated to dryness.
The residue was washed with chloroform several times. The insoluble ma-
terial was removed by filtration, and the filtrate was concentrated. The
obtained powder was dissolved in hot methanol solution (508C, ca.
1 mL), and was then permitted to stand at room temperature. Recrystalli-
zation from methanol gave colorless block crystals of the lanthanide com-
plexes.
(xantpo)2]: Yield: 0.32 g (49%); 1H NMR (300 MHz,
Complex [EuACTHUNRGTENNUG(hfa)2ACHTUNGTRENNUGN
Preparation of [EuACHTUNGTRENNUNG(hfa)3ACHTUNTGREN(NUGN H2O)2]: Europium acetate monohydrate (5.0 g,
CDCl3, 258C): d=6.74–7.65 (m), 1.88 ppm (s; Me); 31P NMR (200 MHz,
[D6]acetone, 258C): d=ꢀ92.12 (2P), ꢀ98.86 ppm (2P); IR (ATR): n˜ =
13 mmol) was dissolved in distilled water (20 mL) in a 100 mL flask. A
solution of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (7.0 g, 34 mmol) was
added dropwise to the solution. The reaction mixture produced a precipi-
tation of white yellow powder after stirring for 3 h at room temperature.
The reaction mixture was filtered, and the resulting powder was recrys-
tallized from methanol/water to afford colorless needle crystals of the
title compound. Yield: 9.6 g (95%); IR (KBr): n˜ =1650 (st, C=O), 1145–
1653 (st, C=O), 1137 (st, P=O), 1095–1251 cmꢀ1 (st, C-O-C and st, C F);
ꢀ
ESI-MS: m/z: calcd for C88H66EuF12O10P4 [Mꢀ
A
1787.264; elemental analysis calcd (%) for C93H67EuF18O12P4·1.5CHCl3
(1994.25): C 52.22, H 3.18; found: C 52.11, H 3.25.
Complex [SmACTHUNRGTENNUG(hfa)2ACHTUNGTRENNUGN
(xantpo)2]: Yield: 0.79 g (46%); 1H NMR (500 MHz,
1258 cmꢀ1 (st, C F); elemental analysis calcd (%) for C15H7EuF18O8
ꢀ
[D6]acetone, 258C): d=5.81–8.09 (m), 1.67 (s; Me), 1.52 ppm (s; Me);
31P NMR (200 MHz, [D6]acetone, 258C): d=33.03 (2P), 32.80 ppm (2P);
IR (ATR): n˜ =1653 (st, C=O), 1138 (st, P=O), 1100–1252 cmꢀ1 (st, C-O-C
(809.91): C 22.48, H 0.88; found: C 22.12, H 1.01.
Preparation of [SmACHTUNGTRENNUNG(hfa)3ACHTUNGTREN(NUGN H2O)2]: Samarium acetate tetrahydrate (5.0 g,
13 mmol) was dissolved in distilled water (60 mL) in a 100 mL flask. A
solution of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (10 g, 48 mmol) was
added dropwise to the solution. The reaction mixture produced a precipi-
tation of white yellow powder after stirring for 1 h at room temperature.
The reaction mixture was filtered, and the resulting powder was recrys-
tallized from methanol to afford colorless needle crystals of the title com-
ꢀ
and st, C F); ESI-MS: m/z: calcd for C88H66SmF12O10P4 [Mꢀ
1786.257; found: 1786.261; elemental analysis calcd (%) for
C93H78SmF15O15P4 (1995.33): C 55.99, H 3.94; found: C 55.54, H 3.53.
ACHTUNGTRENNUNG
(hfa)]+:
Complex [EuACTHNUTRGNEUNG
(hfa)3(tBu-xantpo)]: Yield: 0.35 g (66%); 1H NMR
(300 MHz, CDCl3, 258C): d=7.41 (m, 2H; Ar), 7.07 (m, 2H; Ar), 6.83
(m, 2H; Ar), 5.92 (s, 3H; hfa-H), 2.97–3.02 (m, 6H; 2Me), 1.41–1.68 ppm
(m, 36H; 4tBu); 31P NMR (200 MHz, [D6]acetone, 258C): d=68.41 ppm
(2P); IR (ATR): n˜ =1653 (st, C=O), 1138 (st, P=O), 1098–1249 cmꢀ1 (st,
ꢀ
pound. Yield: 8.3 g (82%); IR (ATR): n˜ =3425 (st, O H), 1646 (st, C=
O), 1094–1251 cmꢀ1 (st, C F); elemental analysis calcd (%) for
ꢀ
C15H7SmF18O8 (808.91): C 22.31, H 0.87; found: C 21.92, H 1.10.
ꢀ
C-O-C and st, C F); ESI-MS: m/z: calcd for C41H50EuF12O7P2
Preparation of xantpo: 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene
(1.0 g, 1.7 mmol) was dissolved in dichloromethane (20 mL) in a 100 mL
flask. The solution was cooled to 08C, and then a 30% H2O2 aqueous so-
lution (4.0 mL, 35 mmol) was added. The reaction mixture was stirred at
08C for 4 h and was then washed with water and extracted three times
with dichloromethane. The organic layer was dried over anhydrous mag-
nesium sulfate and concentrated to dryness. Reprecipitation from hexane
[Mꢀ(hfa)]+: 1097.206; found: 1097.206; elemental analysis calcd (%) for
C46H51EuF18O9P2 (1304.19): C 42.38, H 3.94; found: C 42.93, H 4.00.
Complex [SmACTHNUTRGNEUNG
(hfa)3(tBu-xantpo)]: Yield: 0.39 g (53%); 1H NMR
(500 MHz, [D6]acetone, 258C): d=8.06–8.08 (d, J=7.5 Hz, 2H; Ar),
7.73–7.77 (m, 2H; Ar), 7.50–7.53 (t, J=7.5 Hz, 2H; Ar), 6.73 (s, 3H; hfa-
H), 1.83 (s, 6H; 2Me), 0.52–0.55 ppm (d, J=15 Hz, 36H; 4tBu);
31P NMR (200 MHz, [D6]acetone, 258C): d=62.37 ppm (2P); IR (ATR):
1
gave a white powder of the title compound. Yield: 1.1 g (99%); H NMR
n˜ =1653 (st, C=O), 1137 (st, P=O), 1100–1252 cmꢀ1 (st, C-O-C and st, C
ꢀ
(300 MHz, CDCl3, 258C): d=7.58–7.60 (d, J=6 Hz, 2H; Ar), 7.30–7.47
(m, 20H; Ar), 6.94–7.00 (t, J=6 Hz, 2H; Ar), 6.78–6.85 (m, 2H; Ar),
1.69 ppm (s, 6H; 2Me); 31P NMR (200 MHz, CDCl3, 258C): d=33.55
(1P), 30.32 ppm (1P); IR (ATR): n˜ =1190 (st, P=O), 1100–1229 cmꢀ1 (st,
C-O-C); FAB-MS: m/z: 611 [M+H]+.
F); ESI-MS: m/z: calcd for C41H50SmF12O7P2 [Mꢀ
A
found: 1096.200; elemental analysis calcd (%) for C46H51SmF18O9P2
(1303.19): C 42.43, H 3.95; found: C 42.68, H 3.71.
Complex [EuACTHUNRGTENNUG(hfa)3ACHTUNGTRENNUGN
(dpepo)]: Yield: 0.62 g (74%); 1H NMR (500 MHz,
[D6]acetone, 258C): d=7.32–7.64 (m, 22H; Ar), 7.10–7.13 (t, J=7.5 Hz,
2H; Ar), 6.90–6.95 (dd, J=7.5 Hz, 2H; Ar), 6.73 (s, 3H; hfa-H), 6.29–
6.30 ppm (m, 2H; Ar); 31P NMR (200 MHz, [D6]acetone, 258C): d=
ꢀ113.42 ppm (2P); IR (ATR): n˜ =1653 (st, C=O), 1135 (st, P=O), 1098–
Preparation of tBu-xantpo: 4,5-Bis(di-tert-butylphosphino)-9,9-dimethyl-
xanthene (1.0 g, 2.0 mmol) was dissolved in dichloromethane (20 mL) in
a 100 mL flask. The solution was cooled to 08C, and then a 30% H2O2
aqueous solution (4.5 mL, 40 mmol) was added. The reaction mixture
was stirred at 08C for 4 h and was then washed with water and extracted
three times with dichloromethane. The organic layer was dried over an-
hydrous magnesium sulfate and concentrated to dryness. Reprecipitation
from hexane gave a white powder of the title compound. Yield: 0.97 g
1251 cmꢀ1 (st, C-O-C and st, C F); ESI-MS: m/z: calcd for
ꢀ
C46H30EuF12O7P2 [Mꢀ
N
ysis calcd (%) for C51H31EuF18O9P2 (1344.04): C 45.59, H 2.33; found: C
45.76, H 2.11.
526
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 521 – 528