The first europium(III) β-diketonate complex functionalized polyhedral oligomeric silsesquioxane

Article abstract of DOI:10.1002/chem.201303957

The first europium(III) β-diketonate complex functionalized polyhedral oligomeric silsesquioxane (POSS) has been obtained by immobilization of such a complex at a silicon vertex of the POSS cage through the complexation of Eu ³⁺ ions with thenoyltrifluoroacetone-functionalized POSS. The new molecular hybrid material is liquid at room temperature, and shows bright-red emission when irradiated with UV light due to energy transfer from the thenoyltrifluoroacetone ligand to the coordinated Eu³⁺ ions. Thermal analysis has revealed a significant improvement in the thermal stability of the material compared with tris(2-thenoyltrifluoroacetonate)europium(III) dihydrate, [Eu(TTA)₃]×2 H₂O. In the context of recent advances in printable electronic technology, this novel luminescent organic liquid with the characteristic emission of Eu³⁺ may potentially be useful in the development of next-generation organic devices such as flexible displays. Luminescent organic-inorganic liquid: The first europium(III) β-diketonate complex functionalized polyhedral oligomeric silsesquioxane (POSS) has been realized by the immobilization of such a complex at a silicon vertex of the POSS cage (see scheme). The product is liquid at room temperature and shows bright-red emission when irradiated with UV light owing to energy transfer from the thenoyltrifluoroacetone ligand to the coordinated Eu³⁺ ions. Copyright

Full text of DOI:10.1002/chem.201303957

DOI: 10.1002/chem.201303957
Full Paper
&
Luminescent liquid
The First Europium(III) b-Diketonate Complex Functionalized
Polyhedral Oligomeric Silsesquioxane
Xiaofan Chen, Panning Zhang, Tianren Wang, and Huanrong Li*[a]
Abstract: The first europium(III) b-diketonate complex func-
tionalized polyhedral oligomeric silsesquioxane (POSS) has
been obtained by immobilization of such a complex at a sili-
con vertex of the POSS cage through the complexation of
Eu3+ ions with thenoyltrifluoroacetone-functionalized POSS.
The new molecular hybrid material is liquid at room temper-
ature, and shows bright-red emission when irradiated with
UV light due to energy transfer from the thenoyltrifluoroace-
tone ligand to the coordinated Eu3+ ions. Thermal analysis
has revealed a significant improvement in the thermal stabil-
ity of the material compared with tris(2-thenoyl-
trifluoroacetonate)europium(III) dihydrate, [Eu(TTA)3]·2H2O.
In the context of recent advances in printable electronic
technology, this novel luminescent organic liquid with the
characteristic emission of Eu3+ may potentially be useful in
the development of next-generation organic devices such as
flexible displays.
1. Introduction
composites, while maintaining the combined physical, chemi-
cal, and mechanical advantages of organic–inorganic sys-
tems.[30]
Polyhedral oligomeric silsesquioxane (POSS) has been the sub-
ject of intensive study due to its well-defined rigid inorganic
silica-like core and easily modifiable organic pendant groups. It
gives rise to a family of hybrid molecules with an inorganic
core made up of silicon and oxygen (Si8O12) and eight variable
organic side groups appended at each silicon vertex of the
cage. The overall structures are of size 1–3 nm.[1–6] These POSS
derivatives can be tailored for various applications, such as
coatings,[7] nanocomposites,[8–11] catalysis,[12–14] porous materi-
als,[15–17] drug delivery,[18,19] and self-assembled structures,[20–23]
through appropriate functionalization of the core structure.
Recent studies have demonstrated the importance of POSS de-
rivatives in novel applications in photonics and electrolumines-
cent (EL) devices.[24–29] Improved thermal stability, brightness,
and external quantum efficiency can be obtained for EL de-
vices when semiconducting polymers are covalently linked to
POSS moieties. The solubility, luminescence efficiency, and
color purity of conjugated polymers are also significantly im-
proved. The use of dye-functionalized POSS in highly efficient
and photostable photonic systems has also been reported.[30–34]
These new optical hybrid molecular materials overcome some
of the most important limitations intrinsic to sol–gel hybrid
Lanthanide(III) b-diketonate complexes are interesting lumi-
nescent materials for applications in molecular devices.[35–40]
Processable lanthanide-based luminescent materials can be
realized by incorporating lanthanide complexes into different
types of host matrices, such as zeolites,[41–43] inorganic–organic
hybrid materials,[35,36,39,44–46] liquid crystals,[47,48] ionic liq-
uids,[49–52] ionogels,[53–59] and polymers.[60–62] However, there
have not been any reports on the luminescence of lanthanide
complexes in POSS derivatives. Herein, we report a novel kind
of luminescent organic–inorganic hybrid liquid material, which
was prepared by grafting a europium(III) b-diketonate complex
at a corner vertex of the POSS molecule. This was achieved by
complexation of Eu3+ ions with a thenoyltrifluoroacetone-func-
tionalized POSS, which was in turn synthesized by a corner-
capping reaction of a commercially available trisilanol com-
pound (T-heptasiloxane-triol) with a silylated thenoyltrifluoro-
acetone (Si-TTA), as shown in Scheme 1. To the best of our
knowledge, this is the first report of the covalent grafting of
a europium(III) b-diketonate complex at a corner vertex of mo-
lecular organic–inorganic POSS. It is noteworthy that the ob-
tained europium(III) complex functionalized POSS is a viscous
liquid at room temperature. As is well known, room tempera-
ture luminescent liquids have been regarded as a new genera-
tion of organic soft materials due to their obvious advantages,
such as high stability, versatile optical properties, solvent-free
fluid behavior, and suitability as host materials for dye mole-
cules.[63] The availability of these novel organic liquids, coupled
with recent advances in printable electronic technology, sug-
gests great potential for the development of next-generation
organic devices such as flexible displays.[64] Moreover, a room
temperature ionic liquid consisting of an octacarboxyl POSS
[a] X. Chen, P. Zhang, T. Wang, Prof. Dr. H. Li
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)
Tel : (+86)22-60203674
Fax: (+86)22-60204294
E-mail: lihuanrong@hebut.edu.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201303957.
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Yield: 80%. Elemental analysis calcd (%) for EuC117H222F9O42S3Si24: C
41.40, H 6.58, S 2.83; found: C 42.07, H 6.95, S 2.80; FTIR (KBr): n˜ =
2952, 2921, 2870, 1614, 1530, 1509, 1470, 1415, 1366, 1329, 1169,
1080 cmꢀ1
.
Characterization
1H NMR spectra were recorded at room temperature, using residual
protonated solvents as internal standards. Elemental analysis was
performed on an Elementar Vario EI system. UV/Vis spectra were
recorded on a Varian Cary model 50 UV/Vis spectrophotometer. In-
frared (IR) spectra were obtained on a Bruker Vector 22 spectrome-
ter in the range n˜ =400–4000 cmꢀ1 at a resolution of 4 cmꢀ1 (128
scans were collected). Samples for thermogravimetry (TG) studies
were transferred to open platinum crucibles and analyzed using
a TA Instruments model SDT-TG Q 600 system at a heating rate of
58Cminꢀ1 29Si NMR spectra were measured on a Varian Infinity
.
plus 300 NMR spectrometer from sample solutions in DMF. The
repetition time was 60 s. XRD measurements were performed on
an X-ray powder diffractometer (BRUKER D8 Focus) employing
CuKa radiation (l=1.5418 ꢁ), operating at 40 kV and 40 mA.
Steady-state luminescence spectra and fluorescence lifetimes were
measured on an Edinburgh Instruments model FLS920P spectro-
meter, with a 450 W xenon lamp as the steady-state excitation
source, a double-excitation monochromator (1800 linesmmꢀ1), an
emission monochromator (600 linesmmꢀ1), and a semiconductor-
cooled Hamamatsu model RMP928 photomultiplier tube. The over-
all luminescence quantum yield was determined by an absolute
method on the aforementioned Edinburgh Instruments FLS920P
using an integrating sphere (150 mm diameter, BaSO4 coating).
Scheme 1. Synthesis of the thenoyltrifluoroacetone-functionalized POSS,
POSS-TTA.
anion and an imidazolium cation has recently been report-
ed.[65]
2. Experimental Section
3. Results and Discussion
Materials
Thenoyltrifluoroacetone-functionalized POSS (POSS-TTA) was
easily obtained by a very simple procedure,[13] which involved
reaction of T-heptasiloxane-triol and Si-TTA at reflux for 4.5 h
under an inert gas atmosphere. The product was obtained as
a viscous liquid after evaporation of the solvent and repeated
washing with MeOH. Reaction of POSS-TTA with EuCl3·6H2O in
a 3:1 molar ratio afforded (POSS-TTA)3Eu as a novel lumines-
cent organic–inorganic hybrid material, existing as a viscous
liquid at room temperature.
2-Thenoyltrifluoroacetone (99%, Aldrich), 3-chloropropyltriethoxysi-
lane (97%, Aldrich), and tricyclo[7.3.3.15,11]heptasiloxane-3,7,14-
triol-1,3,5,7,9,11,14-heptakis(2-methylpropyl) (T-heptasiloxane-triol,
Aldrich) were used as received. Eu2O3 was purchased from Shang-
hai Yuelong. Europium chloride hexahydrate (EuCl3·6H2O) was ob-
tained by dissolving Eu2O3 in hydrochloric acid (37%), removing
the excess acid by dilution with water, and concentrating to dry-
ness; this process was repeated several times. The triethoxysilylat-
ed molecule (Si-TTA) was synthesized and characterized according
to the reported method.[66]
The IR spectrum of commercial T-heptasiloxane-triol (Fig-
ure 1a) shows peaks at n˜ =3000–2700 and 1480–1200 cmꢀ1
,
Synthesis of POSS-TTA: In a typical synthesis, a solution of Si-TTA
(229.0 mg) in THF (1 mL) was added to a solution of T-heptasilox-
ane-triol (402.5 mg) in CHCl3 (30 mL). The mixture was heated at
608C for 4.5 h under the protection of an inert gas atmosphere.
After concentration and washing with methanol, a colorless viscous
liquid was obtained. 1H NMR (400 MHz, CDCl3): d=5.911 (t, 1H),
5.380 (t, 1H), 3.119 (s, 2H), 3.002 (d, 1H), 1.798 (m, 9H), 1.310 (m,
2H), 0.905 (d, 42H), 0.538 ppm (d, 16H); elemental analysis calcd
(%) for C39H74F3O14SSi8 (1080.66): C 43.34, H 6.89, S 2.96; found: C
42.72, H 7.02, S 2.90.
which can be assigned to the stretching and bending modes
of the isobutyl moieties. In addition, an intense peak at
n˜ =1110 cmꢀ1 can be attributed to asymmetric stretching of Si-
Synthesis of the molecular organic–inorganic hybrid material
(POSS-TTA)3Eu: A solution of POSS-TTA (0.153 mmol) in CHCl3
(5.0 mL) was added to a solution of EuCl3·6H2O (0.051 mmol) in
EtOH (5.0 mL). The reaction mixture was heated at 708C under stir-
ring overnight. The solvents were then evaporated, leaving a vis-
cous liquid. The liquid product was dried under vacuum at 608C
overnight. (POSS-TTA)3Eu was thereby obtained as viscous liquid.
Figure 1. FTIR spectra of a) T-heptasiloxane-triol, b) POSS-TTA, and c) Si-TTA.
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O-Si, and the band at n˜ =802 cmꢀ1 can be assigned to Si-C
rocking.[67] Two bands at n˜ =3250 and 890 cmꢀ1 may be as-
signed to stretching and bending of Si-OH, respectively, which
were no longer seen in the IR spectrum of POSS-TTA (Fig-
ure 1b), indicating that the cage was completely condensed.[68]
Furthermore, new bands at n˜ =1617 and 1530 cmꢀ1 are ob-
served in Figure 1b. By comparison with the IR spectrum of Si-
TTA (Figure 1c), these may be attributed to the C=O and C=C
stretching vibrations of TTA moieties from POSS-TTA.[66] The
1H NMR spectrum of POSS-TTA features peaks at d=0.534 (m,
16H), 0.939 (m, 42H), 1.167 (m, 2H), 1.799 (m, 9H), 2.502 (t,
1H), 3.290 (t, 2H), 7.080 (t, 1H), and 7.634 ppm (d, 2H), con-
firming the formation of the final product.
The 29Si NMR spectrum of POSS-TTA (Figure 2) features three
signals at d=ꢀ65.7, ꢀ67.05, and ꢀ69.37 ppm, which can be
assigned to the Si atom bonded to the diketone group, the Si
atoms adjacent to the diketone-substituted Si, and the remain-
Figure 4. TG and DTA curves of a) POSS-TTA, b) (POSS-TTA)3Eu, and c) [Eu-
(TTA)3]·2H2O.
Figure 2. 29Si NMR spectrum of POSS-TTA showing peak deconvolution.
ing Si atoms, respectively.[69] The silsesquioxane cage was also
investigated by XRD analysis and the XRD pattern of POSS-TTA
is shown in Figure 3. Two peaks are observed in the XRD pat-
tern: the sharper one at 2q=7.88 with a d-spacing of 12.95 ꢁ
corresponds to the diameter of the POSS-TTA cage, and the
much broader peak at 2q=19.08 with a d-spacing of 5.19 ꢁ is
due to an amorphous structure arising from a loose molecular
packing, which is caused by the substitution of isobutane by
the diketone moiety.[70]
The thermal analysis curve of POSS-TTA is shown in Fig-
ure 4a. A total mass loss of 65.41% was observed. Decomposi-
tion occurred in two main steps. The first step with maximum
mass loss rate at around 2808C can be attributed to the de-
composition of TTA moieties. The second step, starting at
3008C and ending at 6108C, can be ascribed to decomposi-
tions of the isobutyl groups and the Si-O-Si structure of the
cage; the maximum mass loss rate for this step is at 3708C. A
horizontal thermal curve was observed above 6108C, corre-
sponding to a residue yield of 44.23%, a value in good agree-
ment with that expected for the formation of SiO2 (calcd
44.21%). The TG curve of the molecular hybrid material (POSS-
TTA)3Eu, shown in Figure 4b, reveals two decomposition
stages with maximum mass loss rates at 320 and 4208C, re-
spectively. No obvious mass loss can be observed before
2708C, indicating an absence of residual solvent and/or coordi-
nated water molecules in (POSS-TTA)3Eu. In the TG curve of
[Eu(TTA)3]·2H2O (Figure 4c), three main decomposition stages
with maximum mass loss rates at 110, 265, and 5008C, respec-
tively, can be observed. The first stage (4.2%) corresponds to
the removal of coordinated water molecules, and the second
and third stages (75.2%) can be attributed to decomposition
of the TTA ligand (calcd 77%). A plateau is seen above 8008C,
implying the formation of stable Eu2O3 (21.36%), which is in
good agreement with the calculated amount for [Eu-
(TTA)3]·2H2O (21.79%). Comparison of Figure 4b with Figure 4c
Figure 3. XRD pattern of POSS-TTA.
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shows that the thermal stability of (POSS-TTA)3Eu is significant-
ly improved.
The room temperature electronic spectra of POSS-TTA and
the corresponding europium(III) complex ((POSS-TTA)3Eu) re-
corded in EtOH solution are shown in Figure 5. The absorption
spectrum of POSS-TTA exhibits a broad band in the region l=
200–400 nm, which can be attributed to the singlet-singlet
p!p* enol absorption of the b-diketone moieties, with main
components peaking at l=240, 263, and 334 nm. Upon com-
plexation with europium(III), the peak at 334 nm is red-shifted
to 343 nm due to the formation of larger conjugated chelate
rings.[71]
Figure 6. a) Excitation and b) emission spectra of (POSS-TTA)3Eu. The excita-
5
7
tion spectrum was obtained by monitoring the D0! F2 transition at
613 nm; the emission spectrum was obtained at an excitation wavelength
of 350 nm.
dination environment of the Eu3+ ion is free from an inversion
center.[53] The intensity ratio I(5D0! F2)/I(5D0! F1) was calculat-
ed as 16, implying the formation of a europium(III) complex
between Eu3+ and POSS-TTA since values higher than 10 are
expected for such europium(III) b-diketonate complexes.[72] The
absolute quantum yield of POSS-TTA-Eu was determined to be
0.12 by using an integrating sphere according to the reported
7
7
Figure 5. Absorption spectra of a) POSS-TTA and b) (POSS-TTA)3Eu in EtOH at
1ꢂ10ꢀ5 m.
The excitation and emission spectra of (POSS-TTA)3Eu are
shown in Figure 6. The excitation spectrum obtained by moni-
5
method.[73] The luminescence decay curve of the D0 state was
5
7
5
toring the D0! F2 transition at 613 nm displays a broad band
in the spectral range l=200–400 nm, which can be attributed
to the absorption of POSS-TTA. It is largely overlapped with
the UV absorption spectrum of POSS-TTA shown in Figure 5b,
indicating the occurrence of energy transfer from POSS-TTA to
Eu3+ and confirming the formation of a europium(III) b-diketo-
nate complex between POSS-TTA and Eu3+ ions (Scheme 2).
Excitation of POSS-TTA-Eu at 350 nm gives rise to characteristic
metal-centered Eu3+ emissions at 580, 592, 613, 650, and
found to be mono-exponential (Figure S1), and the D0 excit-
ed-state lifetime of Eu3+ in POSS-TTA-Eu was determined to be
0.558 ms. This is much longer than the lifetime of [Eu-
(TTA)3]·2H2O (t=0.333 ms, calculated from the mono-exponen-
5
tial decay curve displayed in Figure S2). The increased D0 ex-
cited-state lifetime of Eu3+ in POSS-TTA-Eu compared with that
in [Eu(TTA)3]·2H2O can be rationalized in terms of confinement
of the organic ligand TTA around the POSS core and the ab-
sence of coordinated water molecules in the POSS-TTA-Eu
complex. The good luminescence properties of the liquid ma-
terial, such as long lifetime and high color purity, together
with its good thermal stability and processability, make it
highly promising for use in flexible electronic applications.[63]
5
7
702 nm, which can be assigned to the D0! FJ (J=0–4) transi-
tions, respectively. The spectrum is dominated by the hyper-
5
7
sensitive transition D0! F2, which is responsible for the red
emission color shown in Scheme 2b, suggesting that the coor-
Scheme 2. a) The chemical structure of (POSS-TTA)3Eu, and b) a digital photograph taken under UV light (lmax =365 nm).
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4. Conclusion
In summary, a novel thenoyltrifluoroacetone-functionalized
POSS, named POSS-TTA, has been synthesized by corner-cap-
ping of a commercially available partially condensed trisilanol
isobutyl POSS with a silylated thenoyltrifluoroacetone. The ob-
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plexation of POSS-TTA with Eu3+ ions results in a red-emitting
molecular organic–inorganic hybrid liquid material, which
shows significantly improved thermal stability compared with
[Eu(TTA)3]·2H2O. The good luminescence properties of the
liquid material, such as long lifetime and high color purity, to-
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This work was financially supported by the National Key Basic
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Keywords: europium(III) b-diketonate complex
·
hybrid
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