Chemistry - A European Journal
10.1002/chem.201605054
FULL PAPER
added dropwise at -78°C. The mixture was gradually brought to room
temperature, and stirred for 14 h. The product was extracted with ethyl
acetate, the extracts washed with brine three times and dried over
Preparation
of
Tris(hexafluoroacetylacetonato)euro-pium
Dihydrates [Eu(hfa)
3
2 2
(H O) ]: Europium acetate monohydrate (5.0 g, 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
4
anhydrous MgSO . The solvent was evaporated, and resulting residue
was washed with acetone and ethanol several times. The obtained white
solid and dichloromethane (ca. 40 mL) were placed in a flask. The
added dropwise to the solution. The reaction mixture produced a
precipitation of white yellow powder after stirring for 3 h at room
temperature. The reaction mixture was filtered, and the resulting powder
was recrystallized from methanol/water to afford colorless needle crystals
2 2
solution was cooled to 0°C and then 30% H O aqueous solution (5 mL)
was added to it. The reaction mixture was stirred for 2 h. The product
was extracted with dichloromethane, the extracts washed with brine three
–
1
of the titled compound (9.6 g, 95%). IR (KBr): 1650 cm (st, C=O),
–
1
times and dried over anhydrous MgSO
4
. The solvent was evaporated to
1145-1258 cm
(st, C–F); elemental analysis calcd (%) for
afford a white powder. Recrystallization from dichloromethane gave white
15 7 8
C H EuF18O
(809.91): C 22.27, H 0.87; found: C 22.12, H 1.01.
1
3
crystals of the titled compound (1.1 g, 33%). H NMR (400 MHz, CDCl ,
–
1
2
5°C): δ = 7.66-7.81 (m, 16H), 7.45-7.60 (m, 12H); IR(KBr): 1120 cm
Preparations of [Eu(hfa)
3
(dpbp)]
n
coordination polymer: The dpbp
(H O) ] (178 mg, 0.22 mmol)
+
(
st, P=O); ESI-MS: m/z = 555.2 [M+H] ; elemental analysis calcd (%) for
: C 77.97, H 5.09; found: C 77.49, H 5.20.
ligand (120 mg, 0.22 mmol) and [Eu(hfa)
3
2
2
36 28 2 2
C H O P
were dissolved in methanol (20 mL). The solution was refluxed while
stirring for 8 h, and the reaction mixture was concentrated to dryness.
The resulting powder was washed with chloroform for several times. The
powder was dried to afford a white powder. A single crystal suitable for
Preparation of 1,3,5-tris(4-diphenylphosphorylphenyl) benzene
tppb): A solution of n-BuLi (7 mL, 1.6 M hexane, 11 mmol) was added
(
III
dropwise to a solution of 1,3,5-tris(4-bromophenyl)benzene (2.0 g, 3.7
mmol) in dry THF (40 mL) at –78°C. The addition was completed in ca.
X-ray structural determination of Eu coordination polymer was obtained
by the diffusion method of methanol–chloroform solution at room
1
0 min during which time a white yellow precipitate was formed. The
temperature. [Eu(hfa)
3
(dpbp)]
n
(196 mg, 67%; for monomer). IR (KBr):
–
1
–1
–1
mixture was stirred for 2 h at –10°C, after which a PPh Cl (2 mL, 11
2
1653 cm (st, C=O), 1255-1145 cm (st, C–F), 1127 cm (st, P=O);
+
+
mmol) was added dropwise at –78°C. The mixture was gradually brought
to room temperature, and stirred for 18 h. After the reaction, the product
was extracted with dichloromethane (30 ml × 3), and then washed with
brine for three times. The dichloromethane solution was dried using
ESI-MS: m/z = 1120.08 [Eu(hfa)
2
(dpbp)] , 2447.15 [Eu
2 5 2
(hfa) (dpbp) ] ;
elemental analysis calcd (%) for [C51
found: C 45.59, H 2.49.
8 2 n
H31EuF18O P ]
: C 46.14, H 2.35;
anhydrous MgSO
powder and dichloromethane (ca. 30 mL) were placed in a flask. The
solution was cooled to 0°C and then 30% H aqueous solution (8 mL)
4
and concentrated to dryness. The obtained white
Preparations of [Eu
3
(hfa)
9
(tppb)
2
]
m
coordination polymer: The tppb
(H O) ] (534 mg, 0.66 mmol)
ligand (200 mg, 0.22 mmol) and [Eu(hfa)
3
2
2
2
O
2
were dissolved in methanol (20 mL). The solution was refluxed while
stirring for 6 h, and the reaction mixture was concentrated to dryness.
The resulting powder was washed with chloroform for several times. The
powder was dried to afford a white powder (310 mg, 82%; for monomer).
was added to it. The reaction mixture was stirred for 2 h. The product
was extracted with dichloromethane, the extracts washed with brine for
three times and dried over anhydrous MgSO
evaporated to afford white powder. The crude materials were
separated using a silica-gel chromatography (methanol / ethyl acetate
:5), and titled compound was recovered as a white solid (0.72 g, 28%).
4
. The solvent was
a
–1
–1
–
IR (KBr): 1650 cm (st, C=O), 1625-1575 cm (st, C-C), 1300-1230 cm
1
–1
+
(
st, C-F), 1150 cm (st, P=O); ESI-MS: m/z = 1410.13 [Eu(hfa)
2
(tppb)] ,
4059.45
] ; elemental analysis calcd
: C 47.95, H 2.41; found: C 47.73, H 2.30.
+
+
1
2
379.40
[Eu(hfa)
2
(tppb)
2
] ,
3286.62
2 3
[Eu(hfa) (tppb) ] ,
1
H NMR (400 MHz, CDCl
3
, 25°C): δ = 7.67-7.83 (m, 27H), 7.53-7.61 (m,
+
+
[
Eu
2
(hfa)
5
(tppb)
3
] , 4833.38 [Eu
3
(hfa) (tppb)
8
3
–
1
6
9
5
H), 7.45-7.53 (m, 12H); IR (KBr): 1190 cm (st, P=O); ESI–MS: m/z =
(
%) for [C165
H
99Eu
3
F
54
O
24
P
6
]
n
+
06.26 [M] ; elemental analysis calcd (%) for C60
H
45
O
3
P
3
: C 77.91, H
.12; found: C 78.32, H 5.04.
Preparations of [Eu
3
(hfa)
9
(tpptz)
2
]
n
coordination polymer: The tpptz
(H O) ] (534 mg, 0.66 mmol)
ligand (200 mg, 0.22 mmol) and [Eu(hfa)
3
2
2
Preparation of 2,4,6-tris(4-diphenylphosphorylphenyl-phenyl)-1,3,5-
triazine (tpptz): The 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (0.2, 0.37
mmol) and tetrakis(triphenylphosphine)palladium(0) (14 mg, 0.012 mmol)
were added into a 5 ml of DMF under argon. Triethylamine (0.2 ml, 1.4
mmol) and diphenylphosphine (0.22 ml, 1.3 mmol) were added into the
DMF solution. The reaction mixture was heated to 130˚C for 24 h. After
the reaction, the product was extracted with dichloromethane (30 ml × 3),
and then washed with brine for three times. The dichloromethane
were dissolved in methanol (20 mL). The solution was refluxed while
stirring for 6 h, and the reaction mixture was concentrated to dryness.
The resulting powder was washed with chloroform for several times. The
powder was dried to afford a white powder. (310 mg, 82%; for monomer).
–
1
–1
–1
IR (KBr): 1655 cm (st, C=O), 1595-1439 cm (st, C-N), 1255 cm (st,
–1
+
C-F), 1200 cm (st, P=O); ESI-MS: m/z = 1476.12 [Eu(hfa)
2
(tpptz)] ,
] , 3933.07
(%) for
: C 46.14, H 2.26, N 2.03; found: C 46.20, H
.21, N 2.60. We consider that the elemental analysis is affected by small
+
+
2
249.49 [Eu (tpptz)] , 3024.91 [Eu
2
(hfa)
5
3
(hfa)
8 3
(tpptz)
+
[
[
Eu (hfa) (tpptz) ] ; elemental analysis
3
8
2
calcd
solution was dried using anhydrous MgSO
The obtained white powder and dichloromethane (ca. 30 mL) were
placed in a flask. The solution was cooled to 0°C and then 30% H
4
and concentrated to dryness.
C
159 3 54 6 24 6 n
H93Eu F N O P ]
2
2
O
2
amount of terminal excess units tpptz on the crystal surface.
aqueous solution (8 mL) was added to it. The reaction mixture was
stirred for 2 h. After the reaction, the product was extracted with
dichloromethane (30 ml × 3), and then washed with brine for three times.
Optical Measurements: Absorption and emission spectra of the
lanthanide complexes were measured with
a
JASCO V-670
The dichloromethane solution was dried using anhydrous MgSO
concentrated to dryness. The crude materials were separated using a
silica-gel chromatography (methanol ethyl acetate 1:5), and titled
compound was recovered as a white solid (0.14 g, 43%). H NMR (400
MHz, CDCl , 25°C): δ = 8.79-8.84 (d, 6H), 7.85-7.94 (dd, 6H), 7.67–7.75
m, 12H), 7.44–7.62 (m, 18H); IR (KBr): 1573-1369 cm (st, C=N), 1180
4
and
spectrophotometor, JASCO F-6300-H spectrometer and Horiba Fluorolog
spectrometers, which corrected for the response of the detector system.
The emission quantum yields excited at 370 nm (Φπ-π*) were estimated
using a JASCO F-6300-H spectrometer attached with JASCO ILF-53
integrating sphere unit (φ = 100 nm). The wavelength dependence of the
detector response and the beam intensity of the Xe light source for each
spectrum were calibrated using a standard light source. The emission
spectra are normalized with respect to the magnetic dipole transition
/
1
3
–
1
(
–
1
+
cm (st, P=O); ESI-MS: m/z = 910.25 [M+H] ; elemental analysis calcd
%) for C57 + C (ethyl acetate): C 73.41, H 5.05, N 4.21;
found: C 73.34, H 4.61, N 4.34.
(
H
42
N
3
O
3
P
3
4 8 2
H O
5
7
intensities at 592 nm (Eu:
0 1
D – F ), which are known to be insensitive to
the surrounding environment of the lanthanide ions. Emission lifetimes of
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