Thermo-stable lanthanoid coordination nanoparticles composed of luminescent Eu(III) complexes and organic joint ligands using micelle techniques in water

Article abstract of DOI:10.1246/bcsj.20140202

Strong luminescent nanoparticles composed of lanthanoid coordination polymers using micelle reaction techniques, lanthanoid coordination nanoparticles, are reported. Size of the nanoparticles estimated using dynamic light-scattering measurements were foun

Full text of DOI:10.1246/bcsj.20140202

Thermo-stable Lanthanoid Coordination Nanoparticles Composed
of Luminescent Eu(III) Complexes and Organic Joint Ligands
Using Micelle Techniques in Water
Onodera Hiromitsu,1,2 Takayuki Nakanishi, Koji Fushimi, and Yasuchika Hasegawa*
2
2
2
1Laser Systems Inc., 1-4-1-10 Nijyuyonken, Nishi-ku, Sapporo, Hokkaido 063-0801
2Division of Materials Chemistry, Faculty of Engineering, Hokkaido University,
North-13 West-8, Kita-ku, Sapporo, Hokkaido 060-8628
E-mail: hasegaway@hokudai.ac.jp
Received: July 15, 2014; Accepted: August 21, 2014; Web Released: September 3, 2014
Strong luminescent nanoparticles composed of lanthanoid coordination polymers using micelle reaction techniques,
lanthanoid coordination nanoparticles, are reported. Size of the nanoparticles estimated using dynamic light-scattering
measurements were found to be approximately 66 nm. Lanthanoid coordination nanoparticles were characterized using
ESI-MS spectrometry, XRD measurements, and thermogravimetric analyses (TGA). Emission properties of lanthanoid
coordination nanoparticles were estimated using emission spectra and emission lifetimes. These results indicate that
nanoparticles composed of lanthanoid coordination polymers show effective luminescent properties and thermal stability
such as bulk powders of lanthanoid coordination polymers.
Lanthanoid complexes with narrow emission bands and long
emission lifetimes have been regarded as promising lumines-
frequency and geometric structures in lanthanoid coordination
polymers. We have recently reported thermo-stable lanthanoid
coordination polymers with high emission quantum yield. The
1
9
cent materials for use in electroluminescent optical materials,
2
organic light-emitting diodes (OLEDs), and luminescent
lanthanoid coordination polymers are composed of hfa (hexa-
fluoroacetylacetonate) ligands for suppression of vibrational
3
biosensing applications. At the present stage, various types
4
10
of luminescent lanthanoid complexes have been reported.
relaxation and phosphine oxide ligands for formation of
11
Plastic luminescent materials containing lanthanoid complexes
have been also studied in the field of industrial application,
asymmetric coordination structures. The emission quantum
yield and decomposition point of Eu(III) coordination polymer
appended with dpbp (4,4¤-bis(diphenylphosphoryl)biphenyl)
5
such as luminescent sealing films for solar cells and plastic
6
9
optical waveguides for opto-telecommunication systems.
are found to be 83% and 308 °C, respectively.
Thermal stability of the luminescent plastic materials are
required that allow industrial preparation at temperatures
around 250 °C making them useful in molding materials and
solder dissolution processes for construction of electronic
devices. Industrial molding and soldering processes at high
temperature are be used for modern manufacturing process.
Based on these points, luminescent lanthanoid coordina-
tion polymers have recently received focus as thermally stable
luminescent materials. Lanthanoid coordination polymers are
composed of lanthanoid complex-bridged organic coordination
units periodically. These periodical structures are combined
with chemical bonding such as CH­π and CH­F interactions.
The periodical structures lead to improvement of thermal
stability with suppression of thermal relaxation at high temper-
ature. Previously, Reddy reported thermally stable lanthanoid
coordination polymers with pyridylaminobenzoate deriva-
In general, characteristic tight-stacking structures of lantha-
noid coordination polymers lead to formation of insoluble
compounds, microsized particles, in water and organic sol-
vents. These insoluble microsized particles prevent preparation
of transparent materials for optical use because of multiple light
scattering in the UV­vis region. The nanosized particles of
lanthanoid coordination polymers without multiple light scat-
tering may provide future optical and luminescent materials.
Concerning the preparation of organomolecule nanoparticles,
buildup and breakdown methods have been reported. Nakanishi
and Oikawa have described a reprecipitation method for for-
1
2
mation of perylene nanocrystals. Masuhara and Asahi have
presented a laser ablation method in liquid media for prepara-
1
3
tion of organic dye and pigment nanoparticles. Preparations
of lanthanoid coordination nanoparticles assisted by surface
1
4,15
stabilizers have been reported.
Kimizuka has also success-
7
tives (decomposition point: 450 °C). Guo has also described
metal­organic frameworks composed of Tb(III) ion with 1,4-
fully reported lanthanoid coordination nanoparticles using
1
6
supramolecular networks.
benzenedicarboxylic acid (decomposition temperature:
We here focused on characteristic formation of organo­
nanoparticles using micelles in liquid media, such as prepara-
tion of nanoscaled organic compounds. The preparation of
polystyrene nanoparticles using micelle techniques has been
8
4
00 °C). However, those lanthanoid coordination compounds
show low emission quantum yield of less than 20%. The
emission quantum yield is improved by control of vibration
1386 | Bull. Chem. Soc. Jpn. 2014, 87, 1386–1390 | doi:10.1246/bcsj.20140202
© 2014 The Chemical Society of Japan

methylsilane standard for 1H NMR spectroscopy. Elemental
analyses were performed with a Yanaco CNH MT-6 analyzer.
Mass spectrometry was performed with a JEOL JMS-T100LP.
Size-distribution was measured with a BECKMAN COULTER
DelsaNanoHC. Thermogravimetric analysis (TGA) was per-
formed on a Rigaku TermoEvo TG8120 analyzer. Scanning
electron microscopy (SEM) was performed with a JEOL JSM-
CF3
H
H
H
O
O
O
Eu(III)
2
F3C
3
[
Eu(hfa) (H O) ]
3 2 2
Micelle A
Diethyl ether
CH3
CH3(CH2)7 N +CH3 Br−
CH3
6
510LA (acceleration voltage, 10 kV).
Mixed Micelle C
TMOA
Tris(hexafluoroacetylacetonato)europium
Dihydrate
Mixing
Stirring
[Eu(hfa) (H O) ]. Europium acetate monohydrate (5.0 g, 13
3 2 2
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
H O
2
(
7.0 g, 34 mmol) was added dropwise to the solution. The
O P
P O
reaction mixture produced a white-yellow precipitate after
stirring for 3 h at room temperature. The powder was collected
by filtration and recrystallized from methanol/water to afford
dpbp
O P
P O Eu(III)
Dichloromethane
colorless needle crystals of the title compound, yield 9.6 g
O
O
¹1
(
95%). IR (KBr): 1650 (s, C=O), 1145­1258 cm (s, C­F).
CF3
CF3
O
H
n
3
Anal. Calcd for C H EuF O (809.91): C, 22.48%. H,
15 7 18 8
CH3(CH2)11 O S ONa
Lanthanoid coordination
nanoparticles
2
2.27%. Found: C, 22.12; H 1.01%.
,4¤-Bis(diphenylphosphoryl)biphenyl (dpbp). 4,4¤-Bis-
O
SDS
4
H O
2
(diphenylphosphoryl)biphenyl was synthesized according to a
Micelle B
9
published procedure. A solution of n-BuLi (9.3 mL, 1.6 M
Figure 1. Preparation scheme of luminescent nanoparticles
composed of lanthanoid coordination polymers, [Eu(hfa)3-
hexane, 15 mmol), was added dropwise to a solution of 4,4¤-
dibromobiphenyl (1.9 g, 6.0 mmol) in dry THF (30 mL) at
(dpbp)]n, using micelle techniques in water.
¹
80 °C. The addition was completed in ca. 15 min during
which time a yellow precipitate was formed. The mixture was
reported in the field of polymer science.17 The micelle sizes are
also controlled by concentration and molecular structure of
organo­surfactants in water media.18
allowed to stir for 3 h at ¹1 °C, after which a PPh Cl (2.7 mL,
2
15 mmol) was added dropwise at ¹80 °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 anhydrous
In the present study, strong luminescent nanoparticles com-
posed of lanthanoid coordination polymers, lanthanoid coordi-
nation nanoparticles, are reported. The luminescent nanoparti-
cles are obtained by the polymerization of [Eu(hfa) (H O) ]
MgSO . The solvent was evaporated, and resulting residue was
4
washed with acetone and ethanol several times. The obtained
white solid and dichloromethane (ca. 40 mL) were placed in a
flask. The solution was cooled to 0 °C and then 30% H O
3
2
2
(hfa: hexafluoroacetylacetonate) with joint ligands (dpbp: 4,4¤-
bis(diphenylphosphoryl)biphenyl) in micelles under water. The
particle size is controlled using SDS (sodium dodecyl sulfate)
and TMOA (trimethyl(octyl)ammonium bromide) in water
2
2
aqueous solution (5 mL) was added to it. The reaction mixture
was stirred for 2 h. The product was extracted with dichloro-
methane, the extracts washed with brine three times and dried
(Figure 1). The structure of nanoparticles was characterized
using ESI-MS spectrometry and XRD measurements. The sizes
of prepared micelles were measured using dynamic light-
scattering (DLS) measurements. Emission properties of nano-
sized lanthanoid coordination polymers were estimated using
emission spectra and emission lifetimes. In this study,
lanthanoid coordination nanoparticles are demonstrated.
over anhydrous MgSO . The solvent was evaporated to afford
4
a white powder. Recrystallization from dichloromethane gave
white crystals of the titled compound.
¹
1
1
Yield: 1.1 g (33%). IR(KBr): 1120 cm (st, P=O). H NMR
(270 MHz, CDCl , 25 °C): ¤ 7.67­7.80 (m, 16H, P-C H ,
3
6
5
C H ), 7.45­7.60 (m, 12H, P-C H , C H ). ESI-Mass (m/z) =
6
4
6
5
6
4
+
5
5
55.2 [M + H] . Anal. Calcd for C H O P : C, 77.97; H,
36 28 2 2
Experimental
.09%. Found: C, 77.49; H, 5.20%.
Preparations of Micelle A, Micelle B, Mixed Micelle C,
Materials. Europium acetate monohydrate (99.9%) and
sodium dodecyl sulfate (SDS:99%) were purchased from Wako
Pure Chemical Industries Ltd. 1,1,1,5,5,5-Hexafluoro-2,4-pen-
tanedione and 4,4¤-dibromobiphenyl (>98%), trimethyl(octyl)-
ammonium bromide (TMOA: >98%) were obtained from
Tokyo Kasei Organic Chemicals. All other chemicals and
solvents were reagent grade and were used without further
purification.
and Nanoparticles Composed of Lanthanoid Coordination
Polymers. TMOA (0.5 g, 1.98 mol) was dissolved in dis-
tilled water (10 mL) in a 100 mL flask. Diethyl ether solution
(0.2 mL) of [Eu(hfa) (H O) ] (10 mg, 12.3 ¯mol) was added at
3
2
2
room temperature, resulting in formation of micelle A com-
posed of TMOA and [Eu(hfa) (H O) ] in water. In contrast,
3
2
2
SDS (0.3 g, 1.04 mol) was dissolved in distilled water (10
mL) in a 100 mL flask. Dichloromethane solution (0.2 mL)
of dpbp (10 mg, 18.0 ¯mol) was added at room temperature,
resulting in formation of micelle B composed of SDS and dpbp
in water.
Apparatus. Infrared spectra were recorded with a JASCO
1
FTIR-350 spectrometer. H NMR (270 MHz) spectra were
recorded with a JEOL EX-270 spectrometer. Chemical shifts
are reported in ppm and are referenced to an internal tetra-
Bull. Chem. Soc. Jpn. 2014, 87, 1386–1390 | doi:10.1246/bcsj.20140202
© 2014 The Chemical Society of Japan | 1387

Mixed micelle C was prepared by the micelle fusion of
micelle A (10 mL) with micelle B (10 mL) for 4 h at room
temperature. Obtained micelles A, B, and C were characterized
using DLS measurements. Obtained micelle C were cen-
trifuged at 4000 rpm for 20 min and the white powder of nano-
particles composed of [Eu(hfa) (dpbp) ] were prepared. Nano-
1
00
a)
b)
2
0
0
50
1
3
2 n
particles were washed twice with dichloromethane, and then
characterized using XRD, DLS, and ESI-MS measurements.
0
0
1
10
100
1
10
100
ESI-MS in MeOH: m/z calcd. [Eu(hfa) (dpbp)] 1122.2,
2
Diameter / nm
Diameter / nm
[
[
(
Eu(hfa) (dpbp) ] 1677.4, [Eu(hfa) (dpbp) ] 2452.5; found
2 2 5 2
Eu(hfa) (dpbp)] 1121.1, [Eu(hfa) (dpbp) ] 1676.2, [Eu(hfa) -
2
2
2
5
dpbp) ] 2447.2. XRD and DLS data are explained in result
c)
d)
2
20
20
10
0
and discussion.
Optical Measurements. The emission spectra of the lantha-
noid coordination polymers were measured with a JASCO
F-6300-H spectrometer and corrected for the response of the
detector system. The emission lifetimes of the lanthanoid
10
0
coordination polymers (10 mm in acetone-d ) were measured
1
10
100
6
1
10
100
by using the third harmonic (355 nm) of a Q-switched Nd:
YAG laser [Spectra Physics, INDI-50, full width at half
maximum (fwhm) = 5 ns, ­ = 1064 nm] and a photomultiplier
Diameter / nm
Diameter / nm
e)
(Hamamatsu photonics, R5108, response time 1.1 ns). The
Nd:YAG laser response was monitored with a digital oscillo-
scope (Sony Tektronix, TDS3052, 500 MHz) synchronized
to the single pulse excitation. The emission lifetimes were
determined from the slope of logarithmic plots of the decay
profiles.
200nm
Figure 2. Size distributions of a) micelle A, b) micelle B,
c) mixed micelle C, and d) washed lanthanoid coordination
nanoparticles using DLS measurements. e) SEM image of
washed lanthanoid coordination nanoparticles.
Results and Discussion
Size of Micelles and Lanthanoid Coordination Nano-
particles.
Lanthanoid coordination nanoparticles were
prepared using micelle techniques in water. The synthetic
scheme is shown in Figure 1. Prepared micelle A (TMOA
and [Eu(hfa) (H O) ]), micelle B (SDS and dpbp), and mixed
Structure and Thermal Stability of Lanthanoid Coordi-
nation Nanoparticles. The powder XRD pattern of nano-
particles containing Eu(III) complexes is shown in Figure 3a.
All signals are calibrated by the signal of silicon powder at
28.4°. Observed signals at 7.5, 8.8, 9.4, 10.2, 20.1, and 21.4°
are attributed to the geometric structures of [Eu(hfa) (dpbp)] .
3
2
2
micelle C were characterized using dynamic light-scattering
DLS) measurements. These size distributions are shown in
(
Figures 2a, 2b and 2c (scattering intensities of DLS: see
Supporting Information Figure S1). The maximum distribu-
tions of micelle A and B were calculated to be 14 and 10 nm,
respectively. Distributions of nanoaggregates composed of
micelle A were also observed at around 109 nm (average size).
Size distribution of micelle A is broad, although that of micelle
B is narrow. These size distribution may be dependent on the
hydrophilicity of the materials ([Eu(hfa) (H O) ] and dpbp) and
3
n
We found that the signals of nanoparticles agree with those
1
9
of previously reported [Eu(hfa) (dpbp)] . These results indi-
3
n
cate that the geometric structure of nanoparticles are the same
as those of [Eu(hfa) (dpbp)] (see Supporting Information
3
n
Figure S2). Form these results, prepared nanoparticles contain-
ing Eu(III) complexes are identified as a [Eu(hfa) (dpbp)] .
3
2
2
3
n
surfactants (TMOA and SDS). We found that the maximum
distribution of mixed-micelle C was estimated to be 134 nm
with wide distribution. The larger size of mixed-micelle C
might be caused by reconstruction of micelle shells com-
posed of SDS and TMOA. The reconstruction of micelle shells
leads to formation of [Eu(hfa) (dpbp) ] in micelle C. In order
The thermal stability of nanoparticles composed of lantha-
noid coordination polymers was evaluated using thermogravi-
metric analyses (Figure 3b). The decomposition temperature
of lanthanoid coordination nanoparticles was estimated to be
301 °C, and agreed well with that of bulk powders. We found
that nanoparticles composed of [Eu(hfa) (dpbp)] show effec-
3
2 n
3
n
to analyze formation of nanoparticles of [Eu(hfa) (dpbp) ] ,
tive thermal stability based on the characteristic rigid struc-
3
2 n
9
we separated from nanoparticles excess surfactants SDS and
TMOA using centrifugation with dichloromethane. The par-
ticles without excess surfactants are shown in Figure 2d.
Average particle sizes were estimated to be 66 and 271 nm,
respectively. Lager size distribution might be caused by aggre-
gation of smaller nanoparticles. The SEM image is shown
Figure 2e. We successfully observed formation of nanoparticles
ture of [Eu(hfa) (dpbp)] with CH­π and CH­F interactions.
3
n
The lanthanoid coordination nanoparticles might be useful for
industrial molding and soldering processes at high temperature
for modern manufacturing processes.
Emission Properties of Lanthanoid Coordination Nano-
particles. The emission spectra of lanthanoid coordination
nanoparticles are shown in Figure 4a. Emission bands for the
Eu(III) coordination polymers are observed at 578, 592, 613,
(average size: 66 nm) using micelle reactions in water media.
1388 | Bull. Chem. Soc. Jpn. 2014, 87, 1386–1390 | doi:10.1246/bcsj.20140202
© 2014 The Chemical Society of Japan

5
7
intensities at 592 nm (Eu(III): D ­ F ), which is known to be
a)
0
1
insensitive to the surrounding environment of the lanthanoid
ions. The emission spectra of nanoparticles of lanthanoid
coordination polymers are similar to those of bulk powders of
lanthanoid coordination polymers. This result indicates that
the coordination geometry of lanthanoid coordination nano-
particles agrees well with that of bulk lanthanoid coordination
polymers.
The time-resolved emission profiles of the lanthanoid coor-
dination polymers also revealed single exponential decays with
lifetimes in the millisecond timescale as shown in Figure 4b.
The emission lifetimes were determined from the slopes of the
logarithmic plots of the decay profiles. Emission lifetimes of
nanoparticles were found to be 0.91 « 0.01 ms, which is the
same as that of bulk powders (Figure S4b: 0.91 « 0.01 ms). We
consider that the emission properties of nanoparticles com-
posed of lanthanoid coordination polymers are the same as
those of bulk lanthanoid coordination polymers.
5
20
35
50
2
θ
/ degree
b)
0
-
25
-
50
-
75
Conclusion
0
100
200
300
We successfully prepared lanthanoid coordination nano-
particles composed of luminescent Eu(III) complexes and
organic joint ligands using micelle reaction techniques in water
media. The thermostable nanostructures were characterized
using DLS, XRD, and TGA measurements. Emission prop-
erties of lanthanoid coordination nanoparticles are similar to
those of bulk powders of lanthanoid coordination polymers.
These results indicate that lanthanoid coordination nanoparti-
cles show effective luminescent properties and thermal stability
such as bulk powders of lanthanoid coordination polymers.
Lanthanoid coordination nanoparticles also improve the opti-
cal transmittance because of their decrease of multiple light
scattering in the UV­vis region. Strong luminescent nanoparti-
cles composed of lanthanoid coordination polymers may lead
to the development of new application of future luminescent
materials.
Temperature / °C
Figure 3. a) XRD pattern of lanthanoid coordination nano-
particles composed of [Eu(hfa)3(dpbp)]n. b) TGA curves
of nanoparticles composed of [Eu(hfa)3(dpbp)]n in argon
¹
1
atmosphere at a heating rate of 1 °C min
.
2
0
a)
1
0
0
5
50
600
650
700
This work was partly supported by Grants-in-Aid for
Scientific Research on Innovative Areas of “New Polymeric
Materials Based on Element-Blocks (No. 2401)” (2401) of
Ministry of Education, Culture, Sports, Science and Technol-
ogy (MEXT) of Japan.
Wavelength / nm
0
1
b)
Supporting Information
-
Scattering intensity data (DLS: micelle A, B, C, and washed-
particles), X-ray single crystals data, XRD, TGA emission data
0
0.5
Time / ms
1.0
(
[Eu(hfa)3(dpbp)]n) are available electronically on J-STAGE.
Figure 4. a) Emission spectrum of Eu(III) coordination
nanoparticles composed of [Eu(hfa)3(dpbp)]n in acetone-d6
at room temperature. Excited at 380 nm. b) Emission decay
of nanoparticles composed of [Eu(hfa)3(dpbp)]n in acetone-
d6 at room temperature excited at 355 nm (third harmonic
of a Q-switched Nd:YAG laser: fwhm = 5 ns, ­ =
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1390 | Bull. Chem. Soc. Jpn. 2014, 87, 1386–1390 | doi:10.1246/bcsj.20140202
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