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J Sol-Gel Sci Technol (2011) 58:711715 DOI 10.



Luminescent organicinorganic hybrid materials based on lanthanide containing ionic liquids and sylilated b-diketone
Yige Wang Yu Feng Hongsheng Zhao Quanying Gan Xiaoyan Yu

Received: 4 January 2011 / Accepted: 19 March 2011 / Published online: 2 April 2011 Springer Science+Business Media, LLC 2011

Abstract In this work, we report the luminescent organicinorganic hybrid materials prepared by hydrolysis and condensation of sylilated b-diketone under acid conditions in the presence of carboxyl-functionalized ionic liquid in which Eu3? ions are coordinated to the oxygen atoms of carboxylate groups from the ionic liquids. The obtained materials were characterized with FT-IR, TG and photoluminescence spectroscopy. FT-IR spectra imply that Eu3? ions are still coordinated to the ionic liquid in the hybrid materials. Excitation and emission spectra demonstrate that the energy transfer occurs from the b-diketone molecules covalently bonded with silica to Eu3? ions. The Eu3? (5D0) quantum efciency value of the hybrid materials has been estimated based on the emission spectrum and the value of lifetime. A large value of ratio (16.44) between the intensities of the 5D0?7F2 and 5D0?7F1 transition and high value of 5D0 quantum efciency (51.01%) are obtained. Keywords Ionic liquids Lanthanide Solgel Photoluminescence

1 Introduction The trivalent lanthanide ions display photoluminescence properties that are favorable for optical applications such as ber ampliers and solid-state lasers [13]. However, the luminescence intensity of lanthanide ions is limited by its poor light-absorbing ability due to the Laporte forbidden character and intracongurational nature of the 4f transitions. Organic ligands with large molar absorption coefcients are normally used to coordinate to lanthanide ions, resulting in sensitized emission via the so called antenna effect [4, 5]. These ligands can also protect the lanthanide ions from molecules with high-energy vibrations such as water molecules that can quench lanthanide ion luminescence by radiationless deactivation. Some of the best ligands for these purpose are b-diketonates having aromatic and uorine substituents in terms of high harvest emissions due to the effectiveness of the energy transfer from the ligand to the Ln3? cations [6, 7]. However, in spite of the interesting luminescence features, lanthanide complexes have been excluded from practical applications as tunable solid-state lasers or phosphor devices due to their poor thermal stability and mechanical properties. One acceptable solution to this problem is to immobilize lanthanide complexes in solgel derived silica, resulting in luminescent organicinorganic hybrid materials [814]. The interest in light-emitting lanthanide based organic inorganic hybrid materials has grown considerably during the last decade as they can nd potential applications in tunable lasers, ampliers for optical communications, emitter layers in multilayer light emitting diodes, efcient light conversion molecular devices, UV dosimeters, and light concentrators for photovoltaic devices [8]. Various lanthanide complexes have been immobilized in the silica matrices via the SiC covalent bond through the hydrolysis

Electronic supplementary material The online version of this article (doi:10.1007/s10971-011-2450-7) contains supplementary material, which is available to authorized users.
Y. Wang (&) Q. Gan X. Yu School of Chemical Engineering and Technology, Hebei University of Technology, 300130 Tianjin, China e-mail: Y. Feng The College of Environmental Science and Engineering, Nankai University, 30071 Tianjin, China H. Zhao Chaoyang Health School, Chaoyang, Liaoning 12200, China



J Sol-Gel Sci Technol (2011) 58:711715

and condensation of TEOS and silylated organic ligands that play double roles of both coordinating to lanthanide ions or lanthanide complexes and acting as an organosilane precursor to form the silica network. Among of them, immobilization of b-diketonate complexes in silica and mesoporous materials is highly intensive due to the reasons mentioned above. This is normally achieved either by adduct formation with a heterocyclic molecular immobilized on the matrices or through the modication of b-diketone [1517]. We recently reported a facile way to prepare luminescent organicinorganic hybrid materials through hydrolysis and condensation of silylated bipyridine that can sensitize the luminescence of europium (III) ions in the presence of a carboxyl-functionalized ionic liquid in which the Eu3? ions are coordinated to the oxygen atoms of carboxylate groups [18]. A longer lifetime of Eu3? 5D0 excited state level was obtained in comparison with similar materials without the addition of ionic liquids [11]. In the present work, lanthanide b-diketonate complexes were immobilized in ionic liquid containing hybrid organosilica via SiC bond by hydrolysis and condensation of TTA-Si (scheme 1) in the presence of 3-(5-carboxypropyl)-1-methylimidazolium bromide (IL, Scheme 1)) in which the Eu3? ions are coordinated to the oxygen atoms of carboxylate groups. The thermal stabilities and the luminescence properties of the resulting hybrid materials are analyzed in detail.

960 and 1,172 cm-1, indicating the complete hydrolysis of the TTA-Si precursor. The presence of the broad band at 1,1201,000 cm-1 indicates the formation of siloxane bonds. No aborption band at 1,729 cm-1 attributed to the COOH (Fig. 1c) groups from the ionic liquid can be observed, implying that Eu3? ions are still coordinated to the ionic liquid in the hybrid materials. The band at 1,690 cm-1 can be ascribed to the absorption of CONH groups from Si-TTA. Thermogravimetric analysis was also performed to determine the thermal stability of the hybrid materials. Figure 2 presents the thermogravimetric weight loss curve (TG). Three main degradation steps can be observed from the TG curve. The rst step of weight loss of ca.17.4% below 200 C could be attributed to the desorption of physically absorbed water and residual solvents. The second weight loss of 45.4% in the range of 200600 C can be ascribed to the decomposition of ionic liquid and the organic moieties from Si-TTA. Finally, the slight weight loss beyond 600 C is ascribed to the release of water

2 Results and discussion FT-IR spectrum was rstly employed to characterize the obtained materials, the FT-IR spectra of TTA-Si and the hybrid material Eu@IL-TTA-SiO2 are shown in Fig. 1. The main changes upon hydrolysis and condensation of TTA-Si in europium (III)-containing ionic liquid with respect to the FT-IR spectrum of TTA-Si is the disappearance of characteristic bands of SiOCH2CH3 groups at

Fig. 1 FT-IR spectrum of TTA-Si (a), the hybrid material Eu@ILTTA-SiO2 (b) and the ionic liquid (c)

Scheme 1 Ionic liquid (IL, a) and silylated ligand (TTA-Si, b) used in this study and the digital photo of luminescent hybrid materials irradiated under uv lamp (kmax = 365 nm, c)

Fig. 2 TGA curve of Eu@IL-TTA-SiO2


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formed from the further condensation of silanols in the silica framework. The organicinorganic hybrid materials show an red photoluminescence upon irradiation with UV radiation (scheme 1). The excitation and emission spectrum of the obtained material were measured at room temperature and are shown in Fig. 3. The excitation spectrum obtained by monitoring the 5D0?7F2 emission at 612 nm displays a large broad band between 225 and 450 nm resulting from the p?p* transition of TTA superimposed with a sharp line characteristic of Eu3? energy level. The relatively low intensity of the intra-4f6 transition compared with that of the broad band in the excitation spectrum indicates that Eu3? ions are essentially excited by a sensitized process rather than by direct population of the intra-4f6 levels. The luminescence spectrum was measured with 325 nm as the excitation wavelength, several narrow peaks can be observed and are attributed to the transitions between the 5 D0 excited state and the different J levels of the ground term 7FJ, (J = 04). The 5D0?7F2 emission line at 612 nm dominates the spectrum and this luminescence line is responsible for the red luminescence color. The presence of the forbidden 5D0?7F0 transition indicates that Eu3? ions

are located in a coordination sphere with low symmetry [19]. The 5D0?7F1 transition corresponds to a parityallowed magnetic dipole transition that is independent of the environment. The hypersensitive 5D0?7F2 transition varies strongly with the local surrounding around the Eu3? ions. Its intensity increases when the lattice environment is distorted and contains certain components of noninversion symmetry. [20] The ratio (R) between the intensities of the 5 D0?7F2 and 5D0?7F1 transition therefore can be used as a parameter to probe the asymmetry of the Eu3? sites. The R value here is determined to be 16.44, indicating that the local symmetry groups of the Eu3? chemical environment is not characterized by an inversion centre. The typical decay curve of the hybrid material was measured and can be described as a single exponential (supporting information, Fig. 1s), indicating that all Eu3? ions occupy the same average coordination environment, and the luminescence lifetime is determined to be 0.531 0.001 ms. We also determine the emission quantum efciency (q) of the 5D0 excited state based on the emission spectra and the lifetime of the Eu3? rst excited level by using the following equations according to reference [21]. q can be dened by Eq. 1 if we assuming that only nonradiative and radiative processes are involved in the depopulation of the 5 D0 state. q kr kr knr 1

where kr and knr are the radiative and nonradiative probabilities, respectively. The radiative contribution may be calculated from the relative intensities of the 5D0?7FJ (J = 04) and can be expressed by Eq. 2. The 5D07F5,6 transitions are not taken into account for the calculus of the efciency of the 5D0 level, probably due to their low intensity (compared with the other lines). Kr
4 A01 E01 X S0J S01 J0 E0J

where A01 is Einsteins coefcient of spontaneous emission between the 5D0 and 7F1 level, usually considered to be equal to 50 s-1 when an average index of refraction n equal to 1.506 was considered. E0J and S0J are the energy and the integrated intensity of the 5D0?7FJ transitions, respectively. The obtained data are summarized in Table 1.The q value for the sample is 51.01% that is much higher than the luminescent hybrid materials reported
Table 1 Experimental 5D0 lifetime, calculated radiative and nonradiative 5D0 decay rate, and 5D0 quantum efciency value Sample Fig. 3 Excitation (a) and emission (b) spectrum of the hybrid material Eu@IL-TTA-SiO2 Eu@IL-TTA-SiO2 s (ms) 0.53 kr (ms-1) 0.96 knr (ms-1) 0.92 q (%) 51.01



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previously [18]. In addition, the value is also much higher than that in the SBA-15 materials where europium (III) complexes are immobilized through the silylated ligand TTA-Si [22].

4.3 Characterization Infrared (IR) spectra were obtained on a Bruker Vector 22 spectrometer using KBr pellets for solid samples, from 400 to 4,000 cm-1 at a resolution of 4 cm-1 (16 scans collected), about 2 mg of each compound were mixed with potassium bromide (Merck, spectroscopic grade) nely ground and pressed into pellets. Samples for thermogravimetric studies were transferred to open platinum crucibles and analyzed using a SDTTG Q 600, TA Instrument at a heating rate of 5 C min-1 using dried nitrogen as purging gas. The steady-state luminescence spectra and the lifetime measurements were measured on an Edinburgh Instruments.FS920P spectrometer, with a 450 W xenon lamp as the steady state excitation source, a double excitation monochromator (1,800 lines mm-1), an emission monochromator (600 lines mm-1) and a semiconductor cooled Hamamatsu RMP928 photomultiplier tube. All spectra were obtained at room temperature. All the excitation and emission spectra were corrected.
Acknowledgments This work is nancially supported by the National Natural Science Foundation of China (No. 20871040, No.20901022), Program for New Century Excellent Talents in University (NCET-09-0113), Tianjin Natural Science Foundation (09JCYBJC05700), the Key Project of Chinese Minstry of Education (208016), the Scientic Program of Hebei Province (07215151) and Hebei Province Natural Science Foundation for Distinguished young Scholar (No.B2010000034).

3 Conclusions We have developed new luminescent organicinorganic hybrid material containing both organosilica and ionic liquids that might be connected by Eu3? ions. Further investigation on the luminescence properties of the obtained material shows that the characteristic luminescence of the corresponding Eu3? through the intramolecular energy transfers from the modied ligand (TTA-Si) to the central Eu3? ions. A high ratio (16.44) between the intensities of the 5 D0?7F2 and 5D0?7F1 transition and high value of 5D0 quantum efciency (51.01%) have been obtained. Therefore, the hybrid materials can be expected to have a potential and signicant application in optical and electronic devices in the future. The materials are not only of great interest from an academic viewpoint, but they might also be extremely valuable materials for various applications.

4 Experimental section 4.1 Materials Europium (III) Oxide (99%, ALDRICH), 3-Bromopropanoicacid (98%, ALDRICH), 1-Methylimidazole (99%, J&KCHEMICALLTD), 2-Thenoyltriuoroacetone (99%, J&KCHEMICALLTD) were used as received. 3-(5-carboxypropyl)-1-methylimidazolium bromide (IL) was synthesized according to the published procedure [23] and was dried in vacuum at 70 C overnight before use. TTA-Si was synthesized and characterized according to the published procedure [24]. 4.2 Preparation of Eu@IL-TTA-SiO2 Dissolution of Eu2O3 (0.48 mmol) into carboxyl-functionalized ionic liquid (3.2 mmol) containing 5 mL of water was rstly done according to the reported procedure [25]. Then 0.9 mmol of TTA-Si dissolved in THF was added to the above solution (Eu@IL) followed by the addition of an appropriate5 amount of H2O (pH 2). The mixture was stirred at room temperature for 3 h, the resulting solution was poured into a glass bottle and placed in an oven at 40 C for 2 weeks and an opaque monolith with light-yellow color was obtained and was ground into powdered materials for further study.

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