Luminescent materials of europium(III) coordinated by a terpyridine-functionalized poly(ionic liquid)

Article abstract of DOI:10.1002/ejic.201301168

A new poly(ionic liquid) (Terpy-PIL) carrying a terpyridine group in each repeating unit of the polymer architecture was readily prepared by polymerization of the monomer (Terpy-IL), which was initiated by azobis(isobutyronitrile) (AIBN). The obtained pol

Full text of DOI:10.1002/ejic.201301168

FULL PAPER
DOI:10.1002/ejic.201301168
Luminescent Materials of Europium(III) Coordinated by a
Terpyridine-Functionalized Poly(Ionic Liquid)
Qiaorong Ru,[a] Zhxin Xue,[b] Yige Wang,[a] Yamei Liu,[a] and
Huanrong Li*[a]
Keywords: Ionic liquids / Tridentate ligands / Luminescence / Europium / Lanthanides / Energy transfer
A new poly(ionic liquid) (Terpy-PIL) carrying a terpyridine
group in each repeating unit of the polymer architecture was
readily prepared by polymerization of the monomer (Terpy-
IL), which was initiated by azobis(isobutyronitrile) (AIBN).
The obtained poly(ionic liquid) can coordinate and sensitize
europium(III) ions through numerous chelating terpyridine
moieties, which are linked to the polymer chains. A red-emit-
ting luminescent material was obtained by the complexation
of europium(III) salts with Terpy-PIL, and the luminescence
is due to an energy transfer from the terpyridine moieties to
Eu3+ ions. The luminescence performance of the luminescent
material based on Terpy-PIL, for example the 5D0 quantum
efficiency and the decay time, is much higher than that of
the luminescent material prepared from the monomer Terpy-
IL, which can be ascribed to the confinement of the europi-
um(III)–terpyridine complexes to the polymer architecture.
bilization of ILs within polymers.[25–39] Among such poly-
mers, poly(ionic liquid)s (PILs) have attracted considerable
attention in the field of polymer chemistry and materials
science, because they combine the unique properties of ILs
with a macromolecular architecture. PILs are a special kind
of electrolytes synthesized by polymerization of monomeric
ILs, and they combine the functionality of ILs with the spa-
tial control of IL moieties, which is provided by the polymer
architectures.[26] PILs show obvious advantages, such as en-
hanced mechanical stability, improved processability, du-
rability, etc.,[37,40] which make them suitable for various ap-
plications as solid ion conductors,[41] carbon precursors,[38]
porous materials,[42] CO2 sorbents,[43,44] and dispersants.[37]
The self-assembly of PILs is highly interesting, because they
can find potential application as nanostructured functional
materials.[45–47]
So far, there are no reports about PILs carrying a ligating
moiety in each of the repeating units of the polymers, al-
though TSILs carrying complexing groups have already
been reported and have been employed in metal separation
and extraction processes[14,16,48] and in catalysis after metal
complexation.[49] In the present contribution, we report for
the first time a new PIL with terpyridine moieties incorpo-
rated into the polymer chain. The resulting PIL, a terpyrid-
ine-functionalized poly(ionic liquid) (Terpy-PIL), is ob-
tained by the polymerization of terpyridine-functionalized
IL monomers (Terpy-IL). Compared with the previously re-
ported PILs, one obvious advantage of the new Terpy-PIL
reported by us is the availability of terpyridine groups in
the repeating units of the polymer, as shown in Figure 1.
Terpyridine can bind various metal ions, which impart
many properties including luminescence and electrochemi-
cal, photochemical, or catalytic activity.[50–56] For instance,
Introduction
Ionic liquids (ILs) are organic salts that are composed
of large organic cations combined with various anions.[1–3]
Because of their intrinsic unique properties, such as very
low vapor pressures, a wide liquid range, good electric con-
ductivity, large electrochemical windows, and good solubil-
ity for a wide range of substances, ILs have recently been
widely used in materials science and technology as lubri-
cants,[4] composite materials,[5] media for the synthesis of
nanomaterials,[6–10] luminescent soft materials,[11] electro-
lytes in devices, and so forth.[12] Furthermore, both the cat-
ionic and anionic components of ILs can be easily changed,
and they can therefore be tailored for particular applica-
tions or be designed to have a specific set of properties.[13]
Specific functional groups were introduced in the cations or
anions of ILs, which led to the so-called task-specific ionic
liquids (TSILs).[14–18] However, there is currently a chal-
lenging need to immobilize ILs in solid devices and at the
same time retain their unique properties from the viewpoint
of material applications. Confining ILs within silica matri-
ces through sol–gel processing is a promising way to immo-
bilize ILs, which can give access to transparent, crack-free
silica monoliths.[19–24] Another strategy involves the immo-
[a] Hebei Provincial Key Laboratory of Green Chemical
Technology and High Efficient Energy Saving, School of
Chemical Engineering and Technology, Hebei University of
Technology,
Tianjin 300130, P. R. China
E-mail: lihuanrong@hebut.edu.cn
http://hgxy.hebut.edu.cn/
[b] School of Chemical Engineering, Qingdao University,
Qingdao 266071, China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301168.
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Figure 2. Possible structure of Terpy-PIL@Eu, which shows the co-
ordination of the terpyridine moieties to Eu3+ ions and the energy
transfer as well as a digital photo taken under UV light (λmax
=
365 nm).
Figure 1. Synthesis procedure for Terpy-PIL.
rings. The strong band at 790 cm–1 is due to the C–C bond
between the pyridine rings.[59,60] As revealed in Figure 3b,
similar absorption bands can be observed for the FTIR
spectrum of Terpy-PIL except for the band of the vinyl
group at 1649 cm–1, which has disappeared, and this indi-
cates the completion of the polymerization of Terpy-IL un-
der the experimental conditions.
luminescent materials of polymer covalently grafted with
terpyridine–lanthanide(III) complexes in the side chains
have already been reported.[57,58] However, no luminescent
materials derived from the incorporation of lanthanide
complexes in the side chains of PILs have been reported up
to now. We therefore also report the first luminescent PIL
obtained by the complexation of Terpy-PIL with europi-
um(III) ions. To the best of our knowledge, this is the first
PIL, in which terpyridine–europium(III) complexes are
linked in the polymer chains. A luminescent material re-
sulting from the coordination of europium(III) to the terpy-
ridine-functionalized IL monomer (Terpy-IL) was also pre-
pared to investigate the effect of polymerization on the lu-
minescence behavior of the luminescent materials.
Results and Discussion
The Terpy-PIL was prepared by polymerization of 4Ј-(1-
vinylimidazolyl)-2,2Ј:6Ј,2ЈЈ- terpyridine (Terpy-IL) in meth-
anol at 65 °C for 24 h, which was initialized with AIBN, as
shown in Figure 1. Terpyridines are well-known ligands for
transition-metal and lanthanide complexes, which find wide
applications in supramolecular chemistry, in dye sensitiza-
tion of solar cells, in luminescent materials, in catalysis, and
in extraction. We investigate the applications of Terpy-PIL
in the preparation of luminescent materials, because terpyr-
idine moieties linked to the polymer chain have the ability
to coordinate to and sensitize Eu3+ ions. A luminescent ma-
terial was prepared by stirring a mixture of EuCl3·6H2O
and Terpy-PIL (molar ratio 1:2) in EtOH/DMF at 70 °C
for 5 h. The product was precipitated by addition of diethyl
Figure 3. FTIR spectrum of Terpy-IL (a) and the obtained PIL
Terpy-PIL (b).
The polymerization can be further confirmed by 1H
1
ether and washed with EtOH several times, and it is referred NMR spectra. Comparative H NMR spectra of the ob-
to as Terpy-PIL@Eu. The obtained materials are highly lu- tained PIL and the Terpy-IL together with an assignment
minescent when they are irradiated with UV light, as shown of the resonances are shown in Figure 4. The absence of
in Figure 2. The amount of Eu3+ in Terpy-PIL@Eu was the vinyl hydrogen signals and the presence of sp3-hydrogen
determined to be 13.07% by using the EDTA titration signals in the spectrum of the PIL indicate the complete
method. Moreover, the luminescent material Terpy-IL@Eu polymerization of Terpy-IL. The relative broadening in the
was prepared similarly by reaction of EuCl3·6H2O with NMR spectra of the polymers has been observed previously
Terpy-IL. The amount of Eu3+ in Terpy-IL@Eu was deter- and can be attributed to the lack of solution mobility of
mined to be 12.16% by the same titration method.
the bulky polymer chains.[61] The molecular weight distribu-
The polymerization of the monomers can be simply veri- tions of Terpy-PIL were determined by gel-permeation
fied by FTIR spectra. The band at 1649 cm–1 shown in the chromatography (GPC) [Mn(GPC) = 63939 g/mol, Mw/Mn
FTIR spectrum of Terpy-IL (Figure 3a) is assigned to the = 1.75]. All obtained data were based on a calibration curve
vibration of the vinyl groups. The bands in the range 1610– [logMw vs V (V = retention volume)] constructed by using
1450 cm–1 are ascribed to the terpyridine and imidazolium narrow-molecular-weight-range polystyrene standards.
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terial to be 12.05%, and this value roughly corresponds to
a molar ratio of 2:1 between Terpy-PIL and Eu3+. The co-
ordination of Eu3+ ions to terpyridine moieties in the PIL
can be confirmed by the luminescence data of the lumines-
cent material Terpy-PIL@Eu, which are shown in Figure 6.
Figure 5. TG curve of Terpy-PIL and Terpy-PIL@Eu.
The luminescence data of Terpy-PIL@Eu and Terpy-
IL@Eu are shown in Figure 6. The excitation spectrum of
Terpy-PIL@Eu, recorded in the range 200–470 nm and
monitored at the 5D0Ǟ7F2 hypersensitive transition at
612 nm, displays a large broad band ascribed to the excited
states of the terpyridine moieties in the polymer, which
largely overlaps with the absorption bands of the po-
ly(ionic liquid) Terpy-PIL (Figure S1). This is diagnostic of
the typical sensitization by the terpyridine moieties of the
Terpy-PIL and therefore confirms that Eu3+ ions are sur-
rounded by terpyridine moieties in Terpy-PIL@Eu. The
emission spectrum excited at 340 nm shows characteristics
of the Eu3+ emissions in the 570–725 nm region, and it exhi-
bits well-resolved, sharp peaks, which are due to the transi-
1
Figure 4. H NMR spectrum of Terpy-IL (a) and Terpy-PIL (b).
5
7
tions from the metal-centered D0 excited state to the FJ
Thermogravimetric analyses were performed to deter- ground state multiplet. Maximum peak intensities at 579,
mine the thermal stability of the Terpy-PILs, and the TG 590, 612, 652, and 702 nm are observed for the J = 0, 1, 2,
curves are shown in Figure 5. Three steps of weight loss can 3, and 4 transitions, respectively, and the so-called “hyper-
be observed in the TG curve of Terpy-PIL. The first one sensitive” J = 2 transition is the most prominent feature,
with approximately 4% weight loss below 230 °C is attrib- which is responsible for the brilliant red emission of the
uted to the desorption of physically adsorbed water and luminescent materials, which is shown in Figure 2. The in-
5
residual solvents. The second weight loss (ca. 43%) in the tensity of the D0Ǟ7F2 transition is much higher than that
5
range 230–510 °C can be ascribed to backbone degradation. of the D0Ǟ7F1 transition, and the intensity ratio of the
5
The last one starts at 510 °C and is complete at 650 °C, and 5D0Ǟ7F2 and D0Ǟ7F1 transitions is 5.42, which implies
the observed weight loss is approximately 48%, which can that the coordination environment of the Eu3+ ions is de-
be attributed to the decomposition of terpyridine moieties void of an inversion center.[21] In fact, the ratio is approxi-
attached to the polymer chains. A horizontal thermal curve mately 0.63 for a hydrated Eu3+ species.[62] The coordina-
was observed above 650 °C. Similarly, three decomposition tion of terpyridine in the polymer to Eu3+ ions results in
steps can also be observed in the TG curve of Terpy-PI- the repulsion of water molecules from the coordination
L@Eu, and they can be assigned to the removal of the re- sphere, and, as a consequence, this causes the remarkable
sidual solvents, to the decomposition of the polymer chains, changes in the intensity ratio of the 5D0Ǟ7F2 and 5D0Ǟ7F1
and to the decomposition of the terpyridine moieties, transitions. The presence of water molecules in the coordi-
respectively. Finally, a horizontal thermal curve was ob- nation sphere of the oxophilic lanthanide center has long
served at temperatures exceeding 650 °C, which is due to been recognized to influence the luminescence properties of
the formation of the thermally stable product Eu2O3 lanthanide ions, and it normally leads to reduced lifetimes
(13.95%). The amount of the chelated europium(III) ions for the excited state and to the quenching of any emissions.
was determined from the TG curve of the luminescent ma- No broad emission band of the polymer can be observed
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the coordination of Eu3+ and Tb3+ to polymers containing
terpyridine show obvious reversible thermochromism.[57]
Furthermore, all the aforementiond materials containing
terpyridine–europium(III) complexes show a relatively low
intensity ratio of I(5D0Ǟ7F2)/I(5D0Ǟ7F1) compared to
those of europium(III) β-diketonate complexes, which typi-
cally show values higher than 10[66,67] (even higher than 20
for some cases).[68] The coordination of the PIL to europi-
um(III) tris(2-thenoyltrifluoroacetonate) dehydrate through
a nitrogen atom from the terpyridine can increase the value
of the intensity ratio of I(5D0Ǟ7F2)/I(5D0Ǟ7F1).[42] This
work is in progress in our laboratory.
To further compare the luminescence performances of
Terpy-PIL@Eu and Terpy-IL@Eu, the 5D0 radiative (kr)
and the non-radiative (knr) transition probabilities and the
5D0 quantum efficiencies of both samples were estimated
according to a reported method by using the following
equations, which are based on the emission spectra and the
5
lifetime of the D0 state of the Eu3+ ions.[69] By assuming
that only non-radiative and radiative processes are involved
5
in the depopulation of the D0 state, q can be defined as
shown in Equation (1).
q = kr/(kr + knr)
(1)
Here kr and knr represent the radiative and non-radiative
probabilities, respectively. The radiative contribution can be
obtained from the relative intensities of the 5D0–7FJ (J = 0–
5
4) transitions (the transitions D0–7FJ with J = 5 and 6 are
either not observed or very weak) and can be expressed by
Equation (2).
Figure 6. Luminescence data of the luminescent material Terpy-
PIL@Eu: (a) Excitation spectra, (b) emission spectra, and (c) decay
curves. Excitation spectra were observed at 612 nm, and emission
spectra were obtained upon excitation at 340 nm. Decay curves
were measured at an excitation wavelength of 340 nm and an emis-
sion wavelength of 612 nm.
(2)
Here, A0–1 represents the Einstein coefficient of the spon-
taneous emission between the 5D0 and 7F1 level and is con-
sidered to be 50 s–1. E0–J and S0–J are the energy and the
in the emission spectrum, which implies that the polymer
transfers the absorbed energy effectively to the emitting
level of the Eu3+ ions. The Terpy-IL@Eu material shows
spectral features, which are very similar to those of the
polymer material Terpy-PIL@Eu. The decay curves of
Terpy-PIL@Eu and Terpy-IL@Eu are well-fitted by means
of a single-exponential function (Figure 6c), which indicates
the presence of only one emissive Eu3+ center. The lifetimes
τ are (0.863Ϯ0.003) and (0.522Ϯ0.002) ms for Terpy-
IL@Eu and Terpy-IL@Eu, respectively. This result shows
that the lifetime is significantly prolonged after the polyme-
rization, which might be due to the confinement of the ter-
pyridine–europium(III) complexes within the rigid chains
integrated intensity of the D0–7FJ transitions, respectively.
5
The resulting data are shown in Table 1. The higher value
of quantum efficiency (q) for Terpy-PIL@Eu compared to
that of Terpy-IL@Eu can be attributed to a decrease in the
knr value in the polymer (0.71 ms–1) with respect to that of
Terpy-IL@Eu (1.49 ms–1), as shown in Table 1.
The number of water molecules (nw) in the coordination
sphere of Eu3+ ions can be estimated on the basis of the
empirical formula suggested by Supkowski and De Hor-
rocks Jr. by using Equation (3).[70]
nw = 1.1(kexp – kr – 0.31)
(3)
5
of the polymer architecture. In fact, the grafting of lantha- Here, kexp is the reciprocal value of the D0 lifetime. The
nide complexes to conventional polymers has been fre- numbers of estimated water molecules in the coordination
quently reported. In those cases, an increase in the lifetime sphere of Eu3+ ions in Terpy-PIL@Eu and Terpy-IL@Eu
was also observed.[63,64] Terpyridine was frequently used as are listed in Table 1. The number of water molecules in the
the sensitizer for lanthanide ions in polymers,[52,57] organo- polymer is 0.44, which indicates that most of the water mo-
silica,[59,65] and ionic liquids[48]. The luminescence features lecules coordinated to Eu3+ ions in europium(III) chloride
of these materials are similar to those of the PILs reported hexahydrate have been displaced from the coordination
in this work. Interestingly, luminescent materials based on sphere by the terpyridine in the polymer, as shown in Fig-
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(400 MHz, [D6]DMSO): δH = 9.68 (t, 1 H), 8.76 (t, 4 H), 8.68 (d,
J = 8.0 Hz, 2 H), 8.29 (s, 1 H), 8.06 (t, 4 H), 8.03 (s, 1 H), 7.70 (t,
2 H), 7.56 (t, 2 H), 7.34 (m,1 H),6.03 (d,1 H), 5.59 (s, 2 H), 5.46
(d, 1 H) ppm. C27H22BrN5 (496.17): calcd. C 65.35, H 4.43, N
14.10; found C 64.65, H 5.30, N 13.98.
ure 2. The number of water molecules coordinated to each
Eu3+ ion in the monomeric Terpy-IL@Eu is 1.3, which indi-
cates that less water molecules are coordinated to Eu3+ ions
in the polymer than in Terpy-IL@Eu.
Table 1. Experimental 5D0 lifetime (τ), calculated radiative (kr) and
nonradiative (knr) transition probabilities, quantum efficiency (q),
and the number of coordinated water molecules (nw).
Synthesis of Terpy-PIL: In a Schlenk flask (50 mL), 2 (0.6 g), AIBN
(0.03 g), and dry methanol (12 mL) were mixed. The mixture was
completely deoxygenated by three cycles of a freeze–pump–thaw
procedure and was backfilled with nitrogen. The mixture was then
stirred, and the flask was thermostated in an oil bath at 65 °C for
28 h. After cooling to room temperature, the crude product was
washed with diethyl ether and methanol several times to give Terpy-
PIL as a yellow solid. (C27H22BrN5)n (496.4): calcd. C 65.35, H
Sample
τ [ms] kr [ms–1] knr [ms–1] q [%]
nw
38.79 0.44
22.39 1.3
Terpy-PIL@Eu
Terpy-IL@Eu
0.86
0.52
0.45
0.43
0.71
1.49
4.43, N 14.10; found: C 66.38, H 4.95, N 14.25. IR (KBr): ν =
˜
1610–1450 [ν(C=N)], 790 [ν(C–C)] cm–1. Mn(GPC) = 63939 g/mol,
Mw = 111893 g/mol, Mw/Mn = 1.75.
Conclusions
A
new poly(ionic liquid) with terpyridine moieties
Preparation of Terpy-PIL@Eu: Independent solutions of europi-
um(III) chloride (typically 2 mL, 0.05 mm), and Terpy-PIL (2 mL,
0.1 mm) were first prepared in an EtOH/DMF mixture. The solu-
tions were then mixed, and the mixture was stirred in an oil bath
thermostated at 70 °C for 5 h. The product was precipitated by the
addition of diethyl ether and washed with EtOH several times.
grafted in each of the repeating units of the polymer was
designed and synthesized for the first time in this work. The
obtained terpyridine-carrying poly(ionic liquid) might find
potential applications in various fields, such as molecular
electronics, sensing, extraction, catalysis, optics, supra-
molecular chemistry, and so on, which is due to the pres-
ence of numerous terpyridine moieties, which can bind vari-
ous metal ions. The binding of europium(III) ions to the
poly(ionic liquid) was used as an example to illustrate the
utilization of these PILs as luminescent materials. The lumi-
1
Characterization Methods: H NMR spectra were recorded with a
Bruker ARX 300 spectrometer. IR spectra were recorded with a
Bruker Vector 22 spectrometer in the range 400–4000 cm–1 at a
resolution of 4 cm–1 (16 scans were collected). Gel-permeation
chromatography (GPC) was measured with a PL-GPC220 appara-
nescent material resulting from the coordination of europi- tus (Agilent Technologies) by using DMF as an eluent and poly-
styrene as the standard sample, and the concentration of the sam-
ple was 1 mg/mL, the flow rate was 1.0 mL/min, and the test tem-
perature was 40 °C. Samples for thermogravimetric studies were
transferred to open platinum crucibles and analyzed by using an
SDT-TG Q 600 TA instrument at a heating rate of 5 °C/min–1. The
steady-state luminescence spectra and the lifetimes were measured
with an Edinburgh Instrument FS920P spectrometer with a 450 W
xenon lamp as the steady-state excitation source, a double exci-
tation monochromator (1800 lines/mm–1), an emission monochro-
mator (600 lines/mm–1), and a semiconductor cooled Hamamatsu
RMP928 photomultiplier tube.
um(III) to the new poly(ionic liquid) shows a bright red
emission when it is irradiated by UV light, which makes
them suitable for combinations with UV-light-emitting
LEDs, because they can be excited in the near-UV region.
Experimental Section
Materials: 1-Vinylimidazole (Aldrich 99%), 2-acetylpyridine (Ald-
rich 98%), p-tolualdehyde (Aldrich 98%), and azobis(isobutyron-
itrile) (AIBN) initiator (Aldrich 99%) were purchased and used as
received. 4Ј-(Methylphenyl)-2,2Ј:6Ј,2ЈЈ-terpyridine was synthesized
according to a reported procedure.[71] EuCl3·6H2O was obtained
by dissolving Eu2O3 in hydrochloric acid (37%), and the excess of
the acid was removed by the addition of water and the subsequent
evaporation of the solvent, and this process was repeated several
times.
Supporting Information (see footnote on the first page of this arti-
cle): Absorption spectrum of Terpy-PIL in DMF.
Acknowledgments
This work was financially supported by the National Key Basic
Research Program (2012CB626804), the National Natural Science
Foundation of China (20901022, 21171046, 21271060, 21236001),
the Hebei Province Natural Science Foundation (B2013202243),
the Tianjin Natural Science Foundation (13JCYBJC18400), and
the Educational Committee of Hebei Province (2011141).
Synthesis of 4Ј-[4-(Bromomethyl)phenyl]-2,2Ј:6Ј,2ЈЈ-terpyridine (1):
A
mixture of 4Ј-(methylphenyl)-2,2Ј:6Ј,2ЈЈ-terpyridine (0.4 g,
1.2 mm), N-bromsuccinimide (NBS, 0.3 g, 1.6 mmol), and benzoyl
peroxide (BPO) (0.16 g, 0.6 mm) in dry ethyl acetate (40 mL) was
heated at 78 °C for 3 h. The warm reaction mixture was filtered to
remove the succinimide, and the solvent was evaporated. The crude
product was recrystallized from ethanol to afford a pale-yellow so-
1
lid (yield: 0.458 g, 90%). H NMR (400 MHz, CDCl3): δH = 8.73
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Received: September 10, 2013
Published Online: December 10, 2013
Eur. J. Inorg. Chem. 2014, 469–474
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