Poly(MMA-co-FMA) as a platform for tuning emission by clicking with luminescent lanthanide complexes

Article abstract of DOI:10.1039/C8TC03022G

In this work, we report a facile approach to prepare lanthanide metallopolymers with tunable photoluminescence by Diels-Alder reaction between poly(MMA-co-FMA) and lanthanide complexes. Emission colors including white light can be regulated by varying the feed ratios of the lanthanide complexes. This straightforward strategy gives us access to the construction of metallopolymers.

Full text of DOI:10.1039/C8TC03022G

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ISSN 2050-7526
PAPER
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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
the Hofmeister effects
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Poly(MMA-co-FMA) as a Platform for Tuning Emission by Clicking
with Luminescent Lanthanide Complexes
Yuanyuan Ren,a Jiachun Feng*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
In this work, we reported a facile approach to prepare lanthanide on copolymerizing lanthanide complex monomers containing a
metallopolymers with tunable photoluminescence by Diels-Alder reactive vinyl-containing ligand with another functional
reaction between poly(MMA-co-FMA) and lanthanide complexes. monomer to get metallopolymers.11-14 Unfortunately, the
Emission colors including white light can be regulated by varying polymerizable complex monomers are hard to design and
the feed ratios of lanthanide complexes. This straightforward arduous to polymerize, which results in poor controllability of
strategy gives us access to the construction of metallopolymers.
the amounts of rare earth complexes in polymers. Thus, facile
methods for the fabrication of color tunable Ln3+-complex
grafted polymers are still lacking.
Nowadays photoluminescent lanthanide (Ln3+) complexes
containing metallopolymers have merited intense attention in
lighting sources, chemical sensors and optoelectronic devices,
1-6 owing to unique optical properties of lanthanide complexes,
including sharp and intense luminescence, large Stokes shift,
long excited-state lifetime, and excellent properties of polymer
matrix such as good transparently, superior mechanical
strength, flexibility and ease of processing.7,8 Fine tuning of the
emission color of luminescent materials, especially white-light
emission, is of great significance for optical-device applications.
For lanthanide (Ln3+)-containing metallopolymers, the tunable
emission is generally generated by adjusting ratios of emission
intensity of lanthanide complexes, depending on the
modulation of either chemical factors (Ln3+ concentration and
coordination environment) or physical parameters (excitation
Diels−Alder (D-A) click reaction, a highly selective [4 + 2]
cycloaddition between electron-rich dienes and electron-poor
dienophiles, has gained a great deal of attention due to their
high specificity, nearly quantitative yield, and exceptional
tolerance towards a wide range of functional groups and
reaction conditions. This reaction has been found specific
applications for attachment of drugs, ligands, and
biomolecules to polymeric materials to obtain functional
polymers.15-18 However, reported examples focused on the
preparation of Ln3+ polymer by click reaction are very rare,
especially the preparation of color-tunable emitting materials
based on click reaction is not reported in open literatures till
now. Weng et al. attached tris-(benzyltriazolylmethyl) amine
ligand to the polyvinylbenzyl chloride backbone resulted in a
metallo-supramolecular polymer via the copper-catalyzed
azide–alkyne cycloaddition reaction.19 In one of our previous
work, we attempted to couple Eu(DBM)3MP to copolymer of
methyl methacrylate and anthracenylmethyl methacrylate
using D-A click reaction. Although the resultant product only
emitted a single color of red light and the content of
Eu(DBM)3MP complexes in the polymer was low due to steric
hindrance, our work proved that click reaction was a powerful
tool for preparation of lanthanide complex containing
metallopolymer. Given that click reactions allow tailor-made
functional precursors prior to perform a click reaction, if
design and synthesize a “clickable” polymer and “clickable”
lanthanide complexes emitting three primary colors, it may be
expected that tunable photoluminescence emission could be
achieved by D-A reaction.
wavelength
and
temperature).
With
regard
to
non-stimuli-responsive fluorescent metallopolymers, tunable
emissions are usually achieved by adjusting the relative
amount of primary colors. The popular approach for this is to
physically blend two or three lanthanide complexes with
polymers.9 The major drawback, whereas, is the aggregation of
inserted lanthanide complexes which strongly affects the
fluorescence intensity and stability. An alternative approach is
to copolymerize fluorescent lanthanide complex monomers
with monomers of host material, which is able to avoid
aggregation of incorporated metal complexes while
maintaining the photophysical properties.10 During the past
decades, there has been increasing investigations that focus
a.State Key Laboratory of Molecular Engineering of Polymers, Department of
Macromolecular Science, Fudan University, Shanghai 200433, China
Electronic Supplementary Information (ESI) available: Synthesis and preparation of
compounds, supplementary figures. See DOI: 10.1039/x0xx00000x
In this work, we took advantage of D-A click reaction for
tunable emission via anchoring lanthanide complexes emitting
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and 1.5 for P20. The PDIs of the copolymers are iVniewa ArreticlaletOivnelinlye
17
broad range, which is due to chain transfDeOr Io: f10F.M103A9./C8TC03022G
To introduce “clickable” dienophile into lanthanide
complexes to perform a D-A reaction with poly(MMA-co-FMA),
we synthesized MP ligand, a maleimide substituted derivative
of 1,10-phenanthroline (see ESI, for details), used as
dienophile and the second ligand as well to coordinate with
different lanthanide metal ions. To realize tunable emission,
Eu3+ primarily coordinated with dibenzoylmethane (DBM) was
used for red color emission, and Tb3+ primarily coordinated
with 4-benzoylbenzoic acid (p-BBA) was used for green color
emission, respectively. As for blue emission, we skillfully used
2-(2-hydroxyphenyl)benzothiazole (BTZ), a blue emission
source, to coordinate with La3+ to get La(BTZ)3MP complex,
since there is no suitable ligand for sensitization of
blue-emitting lanthanum ion at room temperature under 365
nm excitation wavelength. With MP as clickable groups, three
MP-containing lanthanide complexes Eu(DBM)3MP,
Tb(p-BBA)3MP and La(BTZ)3MP were synthesized, respectively
(see ESI, for details). The successful synthesis of these
complexes was confirmed by Elemental Analysis and FT-IR (Fig.
S5). The corresponding excitation and emission spectra of the
three complexes in DMSO solution excited at 365 nm (room
temperature) were displayed in Fig. 1. For Eu(DBM)3MP, the
emission spectrum (Fig. 1a) exhibited five shape bands at 578,
Scheme
1.
Reaction scheme for the synthesis of Ln3+ complex grafted
poly(MMA-co-FMA)-Ln (Ln = Eu, Tb and/or La) by D-A click reaction.
different colors onto the polymer backbone. Our strategy for
fabrication
metallopolymers involves three following steps (Scheme 1).
Firstly, polymer backbone poly(MMA-co-FMA) having
of
color-tunable
fluorescence
emitting
a
pendent furan groups as a click platform was synthesized.
Secondly, three kinds of lanthanide complexes with MP as
“clickable” dienophile were synthesized emitting red, green
and blue fluorescence, respectively. Thirdly, through D-A
reaction between MP ligand of lanthanide complexes and
furan groups of poly(MMA-co-FMA), light emitting
metallopolymers containing lanthanide complexes could be
obtained. By changing the content of the three complexes
introduced to the platform, light can be adjusted. Specifically,
we can achieve this via D-A reaction by stepwise adding three
kinds of complexes (Route 1) or directly adding different
proportions of complexes (Route 2) to platforms. In this article,
we mainly utilized Route 2 to introduce our strategy.
5
590, 613, 651 and 700 nm related to the D0 - 7FJ transitions of
Eu3+, where J = 0 – 4, respectively.20,21 It was dominated by the
5D0
→
7F2 band at 613 nm, which was responsible for the red
emission color shown in the inset of Fig.1a. For Tb(p-BBA)3MP,
excited at 365 nm resulted in line-shaped emission bands (Fig.
1b) at 488, 543, 584 and 619 nm, respectively, corresponding
to the transitions of 5D4
-
7FJ (J = 6, 5, 4, 3) of Tb3+.22 The
→
dominated 5D4 7F5 transition was responsible for the bright
As for a clickable platform, the tailor-made polymer matrix
containing pendant furfuryl groups was prepared via free
radical random copolymerization of furfuryl methacrylate
(FMA) with methyl methacrylate (MMA). FMA is a high
reactive diene that can react with the dienophile-containing
lanthanide complexes. By adjusting the feed ratios of FMA and
MMA, two kinds of polymers P5 and P20 were synthesized as
platforms for D-A reaction, of which the feed ratios of
MMA/FMA were 5/1 and 20/1, respectively. The compositions
of resultant poly(MMA-co-FMA)s were determined from their
1H NMR spectra (Fig. S1 and Fig. S2), using the integration ratio
of the peaks at 3.5 and 4.9 ppm arising from the CH3 protons
belonging to MMA units and CH2 protons belonging to furan
units, respectively. The ratios of FMA to MMA were 1/5 for P5
and 1/20 for P20, respectively, which were in agreement with
their composition ratios directly calculated from their
corresponding feed ratios, suggesting that the reactivity of
both monomers is roughly the same. The molecular weight
(Mn) and polydispersity index (PDI) for each polymer were
characterized by GPC (Fig. S3 and Fig. S4). The Mn values were
31 kg mol-1 for P5 and 26 kg mol-1 for P20, PDI were 1.9 for P5
Fig.1 Fluorescence excitation and emission spectra of complex Eu(DBM)3MP (a),
complex Tb(p-BBA)3MP (b) and complex La(BTZ)3MP (c), as well as P20-Eu (a’),
P20-Tb (b’) and P20-La (c’) excited at 365 nm in DMSO. The insets show the
photographs under the excitation of a 365 nm hand-held UV lamp.
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green emission color shown in the inset of Fig. 1b. Unlike the
sharp emission lines from Eu3+ and Tb3+ complexes, La(BTZ)3MP
had a broad emission band locating in the blue region
centered at 465 nm (Fig. 1c), which is ascribed to the π-π*
transition of BTZ ligand.23,24 It's worth noting that all three
complexes can match a 365 nm UV chip well.
View Article Online
DOI: 10.1039/C8TC03022G
To demonstrate the effectiveness of D-A reaction in
preparation of metallopolymers, we used P20 as a platform to
click reacted with the three complexes to give monochromatic
red, green and blue light, respectively. Eu(DBM)3MP,
Tb(p-BBA)3MP and La(BTZ)3MP with P20 at equimolar ratio of
reactive groups of MP to furan were efficiently coupled via D-A
Fig. 2 The emission spectra of metallopolymers P5-Tb50Eu1 (a), P5-Tb50Eu1.7 (b),
P5-Tb50Eu1La3 (c) and P5-Tb50Eu1La1 (d) excited at 365 nm. (e) CIE
click reaction to give their corresponding P20-Eu
,
P20-Tb and chromatography of P5-Tb50Eu1 (point A), P5-Tb50Eu1.7 (point B), P5-Tb50Eu1La1
(point C) and P5-Tb50Eu1La3 (point D) at 2.5×10-5 M in DMSO solution (R.T.).
1
P20-La. The adduct of complex and P20 was confirmed by H
NMR (Fig. S6), which shows the peak disappeared completely
of the proton of furan ring at 7.4 ppm and the emergence of
new triplet peak signal at 4.85 ppm assigned to the bridgehead
proton of the cycloadduct CH. As shown in Fig. 1a’, 1b’ and 1c’,
with CIE coordinate of (0.31, 0.40) (point D in Fig. 2e). Fig. 2c
displayed the emission peaks of P5-Tb50Eu1La3 at 460 nm (the
blue emission of La(BTZ)3MP), 488 nm, 545 nm (the green
emission of Tb(p-BBA)3MP) and 589 nm, 615 nm (the red
emission of Eu(DBM)3MP).
the emission colors of metallopolymers P20-Eu, P20-Tb and
P20-La in DMF solution excited at 365 nm were red, green and
blue, respectively, quite similar to their corresponding
complexes. As to the photoluminescence spectra, P20-Eu and
P20-Tb exhibit similar Ln3+-centered emission to that of their
corresponding complexes. Compared with La(BTZ)3MP, a slight
blue shift to 448 nm in metallopolymer P20-La was observed.
The reason may be that the absorbed energy of the polymer
chain is partially passed to the BTZ ligand, resulting in the
decrease of energy loss of the nonradiative transition. 14,25
The color tunability may be realized by adding different
complexes to click with platforms stepwise, as shown in Route
1, Scheme 1. We here demonstrated P5 as a “clickable”
platform to realize color-tunability. Heating the mixture of
Tb(p-BBA)3MP and P5 (molar ratio of 1:2 relatives to reactive
groups) in DMSO, a metallopolymer we denoted P5-Tb
emitting green light was obtained, in which half of the furan
groups were residual for further click reactions with lanthanide
complexes. Upon addition of Eu(DBM)3MP into P5-Tb by Tb/Eu
molar ratio of 50:1, the resulting adduct was metallopolymer
we denoted as P5-Tb50Eu1. When excited at 365 nm, a yellow
As mentioned above, the white light emission is usually high
required in many applicant fields. Based the emission of above
P5-Tb50Eu1La3, we decreased the amount of La(BTZ)3MP to
Tb/Eu/La = 50:1:1. It was found that the resulting adduct we
named as P5-Tb50Eu1La1 emitted white light with CIE
coordinate of (0.33, 0.34) (point C in Fig. 2e) under 365 nm UV
light (Fig. 2d). We summarized the luminescent colors of
metallopolymers with different lanthanide complex ratios in
Table 1. It could be see that, the method of utilizing D-A click
chemistry between platforms and complexes to prepare
tunable fluorescent materials is very effective.
Except for the above route (Route 1), metallopolymer with
tuning emission can also be prepared by adding different
molar ratios of lanthanide complexes to click with the platform
in one-step (Route 2, Scheme 1). We herein prepared a
metallopolymer which had a similar composition with the
white emission P5-Tb50Eu1La1 prepared by stepwise process.
By mixing the three complexes at a molar ratio of Eu/Tb/La =
1:50:0.95 (our intended ratio is 1:50:1. However, the added La
complex was slightly less than expectant in practical operation)
and subsequently heating with P5 together, we got a
metallopolymer named P5-Tb50Eu1La0.95. As expected, its
emission was similar to that of P5-Tb50Eu1La1 prepared by
stepwise-click process and emitted a pure white light (Fig. S7).
The photoluminescence (PL) quantum yield (QY), which is a
principal characteristic of luminescent materials, can quantify
the efficiency of the energy transfer. Thus, we investigated the
QYs of the as-prepared metallopolymer samples (10-5 mol L-1 in
DMSO) under excited at 365 nm. The QYs were 5.40% for
Eu(DBM)3MP, 4.49% for Tb(p-BBA)3MP, 14.57% for La(BTZ)3MP,
6.35% for P20-Eu, 4.08% for P20-Tb, 5.52% for P20-La, 3.47%
for P5-Tb50Eu1, 4.01% for P5-Tb50Eu1.7, 5.24% for P5-Tb50Eu1La1
and 5.89% for P5-Tb50Eu1La3, respectively.
emission was observed. Corresponding fluorescence spectrum
5
shows multiple peaks related to D0
→
7FJ transitions of the
Eu3+ ion and D4
→
7FJ transitions of the Tb3+ ion (Fig. 2a). The
5
CIE coordinate of P5-Tb50Eu1 is calculated to be (0.37, 0.33),
located to the yellow region (point A in Fig. 2e), which shows that
the relative intensities of the red emission from Eu3+ and green
emission from Tb3+ are comparable. Further addition of
Eu(DBM)3MP to P5-Tb50Eu1, leaded to the generation of
metallopolymer we denoted P5-Tb50Eu1.7 (Tb:Eu in 50:1.7
molar ratio) with CIE coordinates of (0.41, 0.38) and giving rise
to orange color emission, as shown by point B in Fig. 2e. The
intensity of emission from Eu3+ was stronger than the intensity
of emission from Tb3+ (Fig. 2b). Finally, we used La(BTZ)3MP
emitting blue color to click with its complementary yellow
emission from P5-Tb50Eu1. After adding to P5-Tb50Eu1 by molar
ratio of Tb/Eu/La = 50:1:3, the color changed from yellow to
greenish-yellow. The resulting adduct we named P5-Tb50Eu1La3
Furthermore, the luminescence decay curves of samples
containing Eu3+ and/or Tb3+ were monitored at characteristic
emission of Eu3+ (5D0) and Tb3+ (5D4) (Fig. S8). By fitting to a
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Table 1. The QYs of Eu, Tb and La complexes and various metallopolymers samples
View Article Online
DOI: 10.1039/C8TC03022G
Approximate color regions QY (%)
Complexes
Samples
Eu(DBM)3MP Tb(p-BBA)3MP La(BTZ)3MP
Eu(DBM)3MP
Tb(p-BBA)3MP
La(BTZ)3MP
P20-Eu
P20-Tb
P20-La
red
green
blue
red
green
blue
green
yellow
orange
white
greenish-yellow
white
5.40
4.49
14.57
6.35
4.08
5.52
4.01
4.33
5.24
5.90
5.89
5.77
1
0
0
0
0
1
0
0.5
0.5
0.5
0.5
0.5
0.5
0
0
1
0
0
0
P5-Tb
P5-Tb50Eu1.7
P5-Tb50Eu1
P5-Tb50Eu1La1
P5-Tb50Eu1La3
0.017
0.01
0.01
0.01
0.01
0.03
0.0095
P5-Tb50Eu1La0.95 0.01
o
1
2
3
4
5
6
7
8
9
double exponential function, the average lifetimes τav we
calculated (Table SI, ESI). The fitting results suggested that th
presence of different coordination environments around th
Eu3+ or Tb3+ ions in these complexes and metallopolymer
Compared to the mono-lanthanide metallopolymer, Eu3+ an
Tb3+ containing
hetero-lanthanide metallopolymers ha
shorter τav of Tb3+ but a longer τav of the Eu3+. In addition, b
3
re
3e2
1
air atmosphere at a heat rate of 20 C min-1. It was found that the
metallopolymers showed slight increase for the Tonset in
comparison with lanthanide complexes, and decomposition
with maxima located at higher temperature interval than that
of complexes (Fig. S9). P5-Tb50Eu1La1 remained stable up to
258 oC, indicating that thermal stability of metallopolymers are
significantly improved. In view of the operation temperatures
of LEDs below 150 oC,29,30 the prepared metallopolymer
Poly(MMA-co-FMA)–Eu–Tb–La is thermally stable enough for
3e3
3s4.
3d5
3d6
3
y
7
comparing the lifetimes of P5-Tb50Eu1
av = 334
s for Tb3+ ) and P5-Tb50Eu1.7
(
(


av = 152.59
av = 391.66


s for Eu33+8
,


s for Eu33+9
,
10 av = 211.54

s for Tb3+), we found that the lifetime of Eu43+0 the fabrication of LEDs.
11 increased, while the lifetime of Tb3+ decreased with the
12 increase of Eu3+ content. It means that there may be energy
13 transfer between Eu3+ and Tb3+ ion.What needs to be pointed
14 out is that the energy level of Tb3+ (5D4 = 20500 cm-1)26 is
41 Conclusions
15 higher than that of Eu3+ (5D = 17500 cm-1)27. Based on decay
42 In summary, this study demonstrates that poly(MMA-co-FMA)
43 obtained by the copolymerization of MMA and FMA can be
44 used as a clickable platform for the synthesis of a series of
45 photofluorescent homometallic and heterometallic lanthanide
46 complexes containing poly(MMA-co-FMA)-Ln metallopolymers.
47 In particular, direct white-light emission (CIE: x = 0.33, y = 0.34)
48 with a quantum yield (5.90%) was achieved by P5-Tb50Eu1La1
49 upon excitation at 365 nm in DMSO. The strategy presented
50 here is universal and give a straightforward access to the
51 preparation of variety of lanthanide metallopolymers, thereby
52 opening new perspectives in the field of synthesis of
53 fluorescent polymers where tunable fluorescence emissions
54 are required.
0
16 lifetimes and excited stated energy levels of related ligands
17 (DBM, MP and p-BBA)28 and lanthanide ions. We proposed a
18 possible energy transfer process in the metallopolymers as
19 shown in Scheme 2: (i) the organic ligand moieties DBM, MP
20 and p-BBA absorb UV light and transiting to the singlet excited
21 state (1π-π*, S ) and then to the triplet state (3π-π*, T ) via
1
1
22 intersystem crossing. (ii) non-radiative energy transfer
23 pathway from the T state of the ligand to excited states of the
1
24 Eu3+ and Tb3+ ion. (iii) In the Eu3+-Tb3+-containing
25 metallopolymers, energy transfer occurs from the Tb3+ centers
26 to Eu3+ centers.
27
The thermal properties of the Ln3+ metallopolymers were
28 investigated by thermogravimetric analysis (TGA) measured under
55 Conflicts of interest
56 There are no conflicts of interest to declare.
57 Acknowledgements
58 This work was financially supported by the National Natural Science
59 Foundation of China (51773040, 21574029).
60 Notes and references
61
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Julian-Lopez and P. Escribano, Chem. Soc. Rev., 2011, 40,
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P. Li, Y. Wang, H. Li and G. Calzaferri, Angew. Chem., Int. Ed.,
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Scheme 2. Scheme of energy transfer in metallopolymers.
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Journal of Materials Chemistry C
Page 6 of 6
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DOI: 10.1039/C8TC03022G
Lanthanide metallopolymers with tunable emission were prepared by skillfully designed
Diels-Alder reaction.