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Deng 2015
Deng 2015
Materials Chemistry C
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assemble into photoluminescent nanoparticles in aqueous solutions and act as an excellent scaffold for
the incorporation of various pigments to emit tunable colors, including white, through Fo
rster resonance
energy transfer with high quantum yield up to 0.80. The directly cast films of these NPs after
evaporation of water exhibit strong colorful emission on both smooth quartz and rough plaster surfaces.
www.rsc.org/MaterialsC
The NP aqueous solutions are ready for ink-jet printing to produce exquisite fluorescent pictures.
1. Introduction
Over the past few decades, conjugated polymers have been
meticulously studied for their versatile applications in electronic
and optoelectronic fields, such as organic memory devices, lightemitting diodes and photovoltaic devices.17 On the one hand,
much research attention is focused on p-conjugated polymers
prepared by Suzuki or Yamamoto coupling reactions which have
satisfactory performance in optoelectronic devices.811 However,
their poor solubility limits further processing and applications.
On the other hand, vinyl backbone polymers with pendant
p-conjugated oligomers are synthesized from styrene- and
methacrylate-based monomers via conventional radical (co)polymerization.1217 These vinyl conjugated polymers have a considerable advantage as they exhibit excellent solubility and easily form
uniform films.18,19 Furthermore, it is feasible to design macromolecular architectures or change the composition to adjust their
electronic and optoelectronic properties, which is a challenge in
the above-mentioned main chain p-conjugated polymers.2027
In the molecular construction of vinyl p-conjugated polymers,
the pendant p-conjugated oligomers are of great importance since
they determine electronic and optoelectronic properties. Polyfluorenes (PFs) are the most interesting pendant p-conjugated
units due to their thermal/chemical stability, high fluorescence
quantum yield and significant charge carrier mobility.2830
Supported by both experiments17,31 and density functional
Scheme 1
Synthesis of PFMA.
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Scheme 2
2. Experimental section
2.1.
Materials
Synthesis of macromonomers
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NaHCO3 was added and the mixture was extracted with dichloromethane. The organic phase was washed with aqueous NaHCO3,
HCl, brine and water, successively. After drying over magnesium
sulfate, the organic phase was concentrated and precipitated in
cold methanol to give 0.38 g (95%) of PMFA. 1H NMR (400 MHz,
CDCl3), d (ppm): 7.95-7.30 (46H, ArH), 6.20 (1H, CH3CQCH2),
5.61 (1H, CH3CQCH2), 5.27 (2H, CH2OH), 2.102.00 (26H,
CH2CH2C3H6CH3, CH3CQCH2), 1.13 (68H, CH2CH2C3H6CH3),
0.78 (58H, CH2CH2C3H6CH3, CH2CH2C3H6CH3).
2.3.
Polymerization
Preparation of nanoparticles
Paper
2.5.
Crosslinking of nanoparticles
Measurements
Fig. 1 1H NMR spectra of PFCHO (A), PFCH2OH (B) and PFMA (C) in
CDCl3.
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Table 1
Entry
[D]0/[F]0/[C]0a
Yield (%)
Mn,SECb
PDIb
D : Fc
PD1
PD2
PD3
PD4
1600 : 4 : 1
800 : 4 : 1
400 : 4 : 1
200 : 4 : 1
20
27
36
28
43 900
44 000
35 800
16 200
1.52
1.45
1.43
1.42
910 : 1
360 : 1
210 : 1
100 : 1
a
The ratios of [DMAEMA]0/[PFMA]0/[CTA]0 in the feed. b Measured by
SEC. c The ratio of [DMAEMA]/[PFMA] in copolymers calculated by
1
H NMR.
Fig. 3
H NMR spectra of PD1 (A), PD2 (B) PD3 (C) and PD4 (D) in CDCl3.
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Table 2 DLS results and photophysical properties of functional scaolds
formed by PD1PD4 in aqueous solution
DLS results
Photophysical parameters
Sample
Diameter
(nm)
PDI
Absorption,
lmax (nm)
Emission,
lmax (nm)
Quantum
yield
PD1
PD2
PD3
PD4
75.0
70.6
64.4
28.3
0.30
0.28
0.28
0.27
370
371
371
371
417,
419,
418,
419,
0.80
0.75
0.74
0.65
441
443
443
443
Fig. 4 UV-Vis and photoluminescence spectra at the excitation wavelength of 370 nm of copolymers PD1 (A), PD2 (B), PD3 (C), PD4 (D) and
macromonomer PFMA (E). The concentrations cPD1PD4 = 2.5 10 3 mg mL 1
and cPFMA = 5 10 6 mg mL 1.
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NP
Composition
PB
PG
PR
PO
PW
PD2
PD2
PD2
PD2
PD2
scaolds
scaolds
scaolds
scaolds
scaolds
without doping
doped with C6 (0.3 wt%)a
doped with NR (0.27 wt%)a
doped with DCM (0.25 wt%)a
doped with C6 (0.15 wt%) and NR (0.2 wt%)a
Diameter (nm)
PDI
70.6
81.9
107.0
96.2
136.7
0.28
0.29
0.35
0.28
0.31
Fig. 6 TEM images of PB (A, undoped PD2 NP), PG (B, NPs containing C6), PR (C, NPs containing NR), PO (D, NPs containing DCM) and PW (E, NPs
containing C6 and NR). The detailed compositions are listed in Table 3.
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and hydrophobic dyes located close to PFMA. Thus, the intraparticle FRET from PFMA units to doped dyes can occur, while
the inter-particle FRET should be negligible since the distance
between the cores of two NPs is much larger than 10 nm.
Successful intra-particle FRET is confirmed by measuring
the photoluminescent behavior of aqueous solutions of NPs, as
shown in Fig. 7A. Their UV-Vis spectra are shown in Fig. S4
(ESI). Upon exciting at 370 nm (excitation wavelength for
PFMA), both the characteristic emission of PFMA and that of
Paper
Fig. 7 Photoluminescence spectra of NPs in aqueous solution (A) and in bulk as films (B). Photos of NPs in solution and their films under sunlight (C and
D) and UV light (365 nm) (E and F). Samples a and a* (PB), b and b* (PG), c and c* (PR), d and d* (PO), and e and e* (PW) represent NPs in solution and in
bulk as films, respectively.
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Fig. 8 1931 CIE coordinate diagram of NPs in solution (A) and in bulk as films (B). All sample names are the same as those given in Fig. 7.
than that in the single component NPs, since the energy transfers
occur simultaneously from PFMA to C6, PFMA to NR, and C6 to
NR. The photoluminescence spectrum of PW shows strong white
emission composed of balanced green, red and blue lights
(Fig. 7A).
The emission stability of PW NP was investigated by comparing a sample stored for three months in the dark with a freshly
prepared one. The PL spectra are shown in Fig. S5 (ESI). As the
emission is almost the same after storage for three months,
excellent stability of the PW NP can be concluded.
As an advantage of aqueous solution, NPs are able to form
homogeneous fluorescent films when being cast directly on the
quartz surface. Their emission spectra and the photograph in
the film form are included in Fig. 7B and F. Similar to the
behavior in aqueous solutions, ecient and steady energy
transfers from PFMA to doped dyes occur in NP films. The
emissions of PR and PO films exhibit a slight blue shift and a
little decrease of intensity compared to the emissions of the
corresponding NPs in solution (Fig. 7A and B). This may be
caused by slight intra-particle phase separation of dyes, which
results in a slight aggregation quenching. Fortunately, this
phenomenon leads to a positive eect on the PW film whose
color output is more balanced than that of PW NP solution. The
1931 CIE coordinates of all the NP solutions and their films are
summarized in Fig. 8. The CIE coordinates of both PW solution
and PW film locate in the white emission region. Moreover, the
CIE coordinates of the film at this particular composition are
found to be (0.30, 0.33), which are very close to the center of
(0.33, 0.33).
3.6. Application of photoluminescent NPs in functional
coating and ink-jet printing
PDMAEMA segments can be crosslinked by tetramethoxysilane
(TMOS).47 It extends the application of NPs as fluorescenceactive coating materials. The crosslinking of interparticles
by TOMS guarantee a tolerant film formed on the surface of
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Fig. 9 Photos of plaster models coated with PB, PG and PR NPs under
sunlight (A and C) and UV light (365 nm) (B and D). The object sizes are
ranging from 5 to 10 cm.
Paper
Fig. 10 Schematic illustration of the ink-jet printing process by using the NP solutions. Photographs of the paper printed with dierent patterns under
sunlight and UV light (365 nm). The first line of the patterns contains four Chinese characters from left to right printed by PB, PG, PR solutions and the
original black ink, respectively. The pattern below is the university badge printed by PB solution.
4. Conclusions
A novel polyfluorene-containing methacrylate macromonomer
(PFMA) is synthesized and polymerized with DMAEMA via
RAFT to random copolymers. NPs in aqueous solution prepared
from the amphiphilic copolymers give out blue emission with
high quantum yields over 80%. These PFMA-involved NPs serve
as functional scaolds to bear various dyes. By incorporating
C6, NR and DCM dyes, photoluminescent NPs emit predominantly green, red and orange light upon excitation. NPs with
white emission are obtained by doping C6 and NR with the
ratio of 3 : 4 into the scaolds. All of the NPs show eective
energy transfer and robust photoluminescence both in solution
and in bulk as thin films. NPs can be painted on plaster models
forming a fascinating fluorescent coating. In another example,
the blue, green and red NP solutions are directly used as
fluorescent inks and processed by an ink-jet printer. We
demonstrate promising applications of the PFMA-containing
polymers and more are in progress.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (No. 21374093). J. L. thanks Prof.
Dr. Thieo E. Hogen-Esch of the University of Southern California
for helpful discussions.
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