Highly Thermostable One-Dimensional Lanthanide(III) Coordination

Article pubs.acs.org/crystal

Highly Thermostable One-Dimensional Lanthanide(III) Coordination Polymers Constructed from Benzimidazole-5,6-dicarboxylic Acid and 1,10-Phenanthroline: Synthesis, Structure, and Tunable White-Light Emission Xue Ma,† Xia Li,*,† Yu-E Cha,† and Lin-Pei Jin‡ †

Department of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China Department of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China

‡

S Supporting Information *

ABSTRACT: Three novel isostructural lanthanide(III) coordination polymers (LnCPs), {[Ln3(bidc)4(phen)2(NO3)]·2H2O}n (Ln = Gd (1), Eu (2), Tb (3); H2bidc = benzimidazole-5,6-dicarboxylic acid, and phen = 1,10-phenanthroline), were synthesized via hydrothermal reaction and characterized. The complexes crystallize in the chiral space group P212121. They possess 1D structures based on lanthanide trinuclear clusters containing Ln(1)O9, Ln(2)O6N2, and Ln(3)O6N2 polyhedra by bidc linkers, and phen and nitrate act as terminal ligands. The bidc and phen ligands provide efficient energy transfer for the sensitization of Eu(III) and Tb(III) complexes. The complexes 2 and 3 emit red and green light, respectively. Lifetimes and quantum yields of luminescence are 0.86 ms and 13.20% for 2 and 0.32 ms and 2.08% for 3. Tuning of white-light emission by adjusting the doping concentration of Eu(III) and Tb(III) ions in the Gd(III) complex was achieved.

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INTRODUCTION White-light-emitting diodes have broad applications in displays and lighting for the purpose of conserving energy and miniaturization of equipment.1 The white-light-emitting materials have been produced through monochromatic, dichromatic, trichromatic, and tetrachromatic approaches.2 Study of tunable white-light-emitting metal coordination polymers (MCPs) has been developed.2g−j White-light-emitting MCPs are candidates for light-emitting devices due to their structural diversity and ligand-dependent luminescence sensitization. Lanthanide (Ln) ions have unique luminescence features, such as high luminescence quantum yield, narrow bandwidth, long-lived emission, and large Stokes shift. These properties make Ln(III) ion emission suitable for biomedical analyses and imaging, lighting, and display applications.3 Studies on the photoluminescence of Ln(III) complexes are extensively designed and investigated. However, tunable white-light emission of Ln(III) complexes has been less reported.2g−i,4 As is known, Eu(III) and Tb(III) complexes emit red and green light, respectively, and are the most intense emitters among the lanthanide series. It is known that owing to the high energy (32150 cm−1) of the Gd(III) ion lowest-lying emission level, sometimes the Gd(III) complex shows ligand-centered visible emission in blue light region, and thus the Gd(III) complex may act as a blue emitter. Therefore, Gd(III), Tb(III), and Eu(III) complexes are incorporated into the resulting whitelight-emitting materials. © XXXX American Chemical Society

We are focusing on aromatic benzimidazole-5,6-dicarboxylic acid (H2bidc) and 1,10-phenanthroline (phen) to construct luminescent coordination polymers. H2bidc is a rigid and conjugated multidentate ligand and possesses two nitrogen and four oxygen donor atoms to construct coordination frameworks with different topology and dimensionality via versatile coordination modes.5 Phen molecule is a good chelating ligand for Ln(III) ions. Especially, phen ligand presents a blue emission under UV excitation. Phen has a high efficiency of light absorption (λ = 264 nm, ε = 33 900 M−1 cm−1), the energy of its triplet excited state (22 100 cm−1) is higher than the lowest emitting level of the Eu(III) (17 500 cm−1) and Tb(III) (20 500 cm−1), but lower than that of Gd(III) (32 150 cm−1).3c So, phen in conjunction with H2bidc is a suitable choice to obtain tunable white-light-emitting lanthanide(III) coordination polymers (LnCPs). This paper reports synthesis, structure of {[Ln3(bidc)4(phen)2 (NO3)]·2H2O}n (Ln = Gd (1), Eu (2), and Tb (3)) and tunable white-light emission of their doped complexes.

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EXPERIMENTAL SECTION

Experimental Detail and Physical Measurements. All reagents were commercially available and were used without further purification. Elemental analyses (C, H, and N) were determined on an Elementar Vario EL analyzer. IR spectra were recorded on a Nicolet Received: May 2, 2012 Revised: September 4, 2012

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dx.doi.org/10.1021/cg300932a | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

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Figure 1. View of the structure of 2: (a) Coordination environments of Eu1, Eu2, and Eu3 ions in 2. Free water molecules and H atoms are omitted for clarity. Symmetry codes: (A) 1.5 − x, 2 − y, −0.5 + z; (B) 1.5 − x, 2 − y, 0.5 + z. (b) 1D chain structure (top) and Eu−O−C−O−Eu doublestranded helices (bottom). Magna 750 FT/IR spectrometer using the KBr pellet technique in the range of 400−4000 cm−1. X-ray diffraction was performed on a PANaytical X’Pert PRO MPD diffractometer for Cu Kα radiation (λ = 1.5406 Å), with a scan speed of 2°·min−1 and a step size of 0.02° in 2θ. The simulated PXRD patterns were obtained from the single-crystal Xray diffraction data. The experimental PXRD patterns are identical with the calculated ones obtained from the single-crystal structures, confirming the phase purity of the bulk samples. The fluorescence spectra were recorded on an FL4500 fluorescence spectrophotometer (Japan Hitachi company) at room temperature. The lifetimes were measured at room temperature on Life Spec-Red Picosecond lifetime spectrometer (Edinburgh Instruments) for complex 1 and FLS920 steady-state and time-resolved fluorescence spectrometer (Edinburgh Instrument) for complexes 2 and 3. The emission quantum yields were measured at room temperature using a quantum yield measurement system Fluorolog-3 (HORIBA company) with a 450W Xe lamp coupled to a monochromator for wavelength discrimination, an integrating sphere as sample chamber, and an analyzer R928P for signal detection. The Commission International de I’Eclairage (CIE) color coordinates were calculated on the basis of the international CIE standards.6 Thermogravimetric analyses (TGA) were carried out using a WCT-1A thermal analyzer under air from room temperature to 1000 °C with a heating rate of 10 °C/min. Synthesis of Complexes 1−3. A mixture of Ln(NO3)3·6H2O (0.4 mmol) (Ln = Gd, Eu, and Tb), H2bidc (0.6 mmol), phen (0.4 mmol), H2O (5 mL), and an aqueous solution of NaOH (2 mol/L, 0.25 mL) was sealed in a Teflon-lined reactor and heated at 170 °C for 3 days. After slow cooling to room temperature, block crystals of the complexes were obtained. Yield: 45.2% for 1, 42.4% for 2, and 49.5% for 3 based on Ln. Complex 1, Anal. Calcd for C60H36Gd3N13O21: C, 41.26; N, 10.42; H, 2.08%. Found: C, 41.25; N, 10.07; H, 2.53%. Selected IR (KBr pellet, cm−1): 3460(w,br), 3079(w), 1612(s), 1529(s), 1467(s), 1408(vs), 1355(s), 1298(m), 1190(m), 1032(m), 962(m), 866(s), 843(s), 795(m), 670(m), 636(w), 417(w). Complex 2, Anal. Calcd C60H36Eu3N13O21: C, 41.63; N, 10.52; H, 2.10%. Found: C, 41.64; N, 10.43; H, 2.54%. Selected IR (KBr pellet, cm−1): 3449(w,br), 3079(w), 1610(s), 1528(s), 1466(s), 1405(vs), 1347(s), 1295(m), 1189(m), 1032(m), 961(m), 865(s), 843(s), 794(m), 669(m), 634(w), 417(w). Complex 3, Anal. Calcd for C60H36Tb3N13O21: C, 41.14; N, 10.40; H, 2.07%. Found: C, 41.02; N, 10.27; H, 2.52%. Selected IR (KBr pellet, cm−1): 3460(w,br), 3078(w), 1613(s), 1529(s), 1466(s), 1406(vs), 1355(s), 1297(m), 1190(m), 1032(m), 962(m), 866(s), 843(s), 794(m), 670(m), 634(w), 417(w). X-ray Crystallography Study. Single-crystal X-ray diffraction data of complexes 1−3 were collected on a Bruker SMART CCD diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The structures were solved by direct methods and refined by full-matrix least-squares on F2 using SHELXS 97 and SHELXL 97 programs.7 All non-hydrogen atoms in the complexes were refined anisotropically. The hydrogen atoms were generated geometrically and treated by a mixture of independent and

constrained refinement. A summary of the crystallographic data and details of the structure refinements are listed.8 Selected bond distances and bond angles are listed in Tables S1−3, Supporting Information.

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RESULTS AND DISCUSSION Description of the Structures. The single-crystal X-ray diffraction reveals that the complexes {[Ln3(bidc)4(phen)2(NO3)]·2H2O}n (Ln = Gd (1), Eu (2), and Tb (3)) are isostructural and crystallize in the chiral space group P212121 (orthorhombic system) with a Flack parameter of 0.02(3); herein only the structure of 2 will be discussed in detail. The phase purity was confirmed by powder X-ray diffraction, as shown in Figure S1, Supporting Information. The asymmetric unit of 2 consists of three crystallographically independent Eu(III) ions, four bidc ligands, two phen ligands, one nitrate anion, and two free water molecules (Figure 1a). The complex 2 consists of an infinite 1D coordination polymer. The bidc ligand coordinates Eu(III) ions in two ways: μ4tetradentate and μ5-pentadentate bridging fashions (Scheme S1, Supporting Information) with ratio of 1:2. The carboxylate groups of the μ4-bidc and μ5-bidc are twisted relative to their benzene rings by 12.9°/43.1° and 17.6°/135.2°, respectively. The terminal phen and nitrate ligands occupy the remaining coordination sites. Each bidc connects three different Eu(III) ions, Eu(1), Eu(2), and Eu(3). Eu(1) is nine-coordinate (Eu(1)O9), while Eu(2) and Eu(3) are similar eight-coordinate (Eu(2)O6N2 and Eu(3)O6N2). Eu(1) is coordinated by six O atoms from three μ5-bidc ligands, one O atom from a μ4-bidc ligand, and two O atoms from chelating nitrate. The Eu(2) is coordinated by five O atoms from three μ5-bidc ligands, one O atom from a μ4-bidc ligand, and two N atoms from chelating phen, while Eu(3) is coordinated by three O atoms from two μ5-bidc ligands, three O atoms from a μ4-bidc ligand, and two N atoms from phen. Eu(1)O9, Eu(2)O6N2, and Eu(3)O6N2 form a trinuclear cluster. As building blocks, the trinuclear clusters are further assembled into 1D chain structure through the COO groups along the c axis, where Eu−O−C−O−Eu doublestranded helices are found (Figure 1b). The distances of Eu1···Eu2 and Eu1···Eu3 ions are 4.168(2) and 4.214(2) Å, respectively. The angle of Eu···Eu···Eu is 127.42°. The pitch of the helix is calculated to be 12.502 Å. The adjacent helical chains form a 3D network by hydrogen bonds and π−π stacking interactions (Figure S2 and Table S5, Supporting Information). The structure of 2 is different from Ln−H2bidc complexes reported in literature6 and is the first example of a 1D chiral chain based on H2bidc ligand in conjunction with B



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biexponential decay curve with τ1 = 1.09 ± 0.02 μs and τ2 = 16.01 ± 0.26 μs (Figure S4a, Supporting Information). The luminescent lifetimes of 2 and 3 are 0.86 and 0.32 ms, respectively (Figure S4b,c, Supporting Information). The luminescent lifetime of 1 is shorter than that of 2 and 3 because 1 is the ligand-based emission. The quantum yields of luminescence for 2 and 3 are 13.20% and 2.08%, respectively. The luminescence lifetimes and quantum yields of 2 and 3 are relatively shorter and lower because the complexes 2 and 3 contain high energy C−H, N−H, and O−H oscillators, which significantly quenche the Eu(III) and Tb(III) emitting states, but are comparable to the reported ones of the LnOFs.3j−l From the above results, we can conclude that bidc and phen ligands are sensitizers for luminescence of 2 and 3. And the complexes 1, 2, and 3 act as blue, red, and green emitter components, respectively. Therefore, by changing the relative amount of Gd(III), Eu(III), and Tb(III) in the doped complexes, a white-light emission can be obtained. The complexes 1, 2, and 3 are isostructural; doped complexes of the pure phase with different Ln(III) doping ratios (Gd(III), Eu(III), and Tb(III)) were obtained. The doped materials are isostructural to the original complexes (1−3) verified by powder X-ray diffraction (PXRD) analysis; their PXRD patterns coincide with the those of 1−3 (Figure S1d, Supporting Information). The emission spectra of the doped materials upon excitation at 376 nm were recorded (Figure 3).

phen ligand. Also, the examples of lanthanide coordination polymers based on polynuclear clusters are limited.9 Luminescent Properties. The luminescent properties of the complexes in the solid state were investigated at room temperature. Under UV excitation at 365 nm for H2bidc and 378 nm for phen, the pure ligands present a blue emission with the bands at 430 nm for H2bidc and 438 nm for phen (Figure S3, Supporting Information). The excitation and emission spectra of 1 display similar spectra to those of the ligands (Figure 2a); no f−f transition emission of the Gd(III) ion was

Figure 2. Excitation (left) and emission (right) spectra of complexes 1 (a), 2 (b), and 3 (c) in the solid state at room temperature.

observed because its lowest-lying emitting level is located at 32 150 cm−13c (corresponding to the 6P7/2 → 8S7/2 transition) and energy transfer from the ligand to 6P7/2 excited state of Gd(III) cation cannot occur. Under excitation at 376 nm, complex 1 presents a blue emission with the band centered at 440 nm, which comes from the π*−π transition of the ligands (Figure 2a, right). The excitation spectra of 2 and 3 were recorded by monitoring at 613 nm for 2 and 544 nm for 3, and the spectra display broad bands centered at 350 nm, which can be attributed to intraligand charge change (ILCT) of the ligands and the ligand-to-metal charge transfer (LMCT) for 210 (Figure 2b, left) and ILCT for 3 (Figure 2c, left). But the sharp excitation peak at 395 nm (Figure 2b, left) is assigned as the 7F0 → 5L6 transition of Eu(III) ion. The emission spectra of complexes 2 and 3 were studied under excitation at 350 nm. Complex 2 displays narrow and characteristic luminescence due to 5D0 → 7FJ (J = 0−4) transitions of Eu(III) ion (Figure 2b, right). The most intense emission at 613 nm is attributed to the 5 D0 → 7F2 (electric-dipole) transition, which is hypersensitive to the coordination environment of the Eu(III) ion and implies a red emission light. The medium-strong emission band at 590 nm corresponds to the 5D0 → 7F1 (magnetic-dipole) transition, which is fairly insensitive to the environment of the Eu(III) ion. The intensity ratio of 14.7 for I(5D0→7F2)/I(5D0→7F1) indicates a low symmetry of the Eu(III) site in 2. Complex 3 shows emission bands at 488, 544, 584, and 619 nm, which correspond to the characteristic 5D4 → 7FJ (J = 6−3) transitions of the Tb(III) ion (Figure 2c, right). The most intense emission at 544 nm corresponds to the 5D4 → 7F5 transition of the Tb(III) ion. The ligand-centered emission bands at about 430 and 438 nm disappeared in the emission spectra of 2 and 3, indicating the efficient ligand-to-Ln(III) ion energy transfer in 2 and 3. The lifetime of luminescence for 1 was measured from the decay profile by fitting with

Figure 3. Emission spectra of the doped complexes excited at 376 nm. A−E(Gd,Tb,Eu%): A(97,2,1), B(97.5,1.5,1), C(98,1,1), D(98.5,0.5,1), and E(99,0.5,0.5).

The emission spectra display essentially the typical 5D0 → 7FJ (J = 0−4) transitions for 2, 5D4 → 7FJ (J = 6−3) transitions for 3, and the broad band centered at 440 nm assigned to ILCT of the ligands in 1. Variations in the relative blue, red, and green emission intensities were observed when the doping ratios of Gd(III), Eu(III), and Tb(III) changed. The CIE chromaticity diagram of these doped materials is listed in Table S7, Supporting Information. It reveals that the emission color of the doped materials can be finely tuned by varying the doping ratio, and white-light emission of the doped material with the molar ratio of 98.5:0.5:1 (Gd(III)/Eu(III)/Tb(III)) was obtained at CIE chromaticity coordinates (0.322, 0.328) (Figure 4D), which is very closed to international pure white light CIE chromaticity coordinates (0.333, 0.333). The excitation wavelength 376 nm locates in the range 290−390 nm of the excitation spectra of 2 and 3. It is something worthy to be mentioned that the excitation wavelength of Ln−bidc− phen doped hybrid materials is longer than that reported for Ln-based MOFs,2g−i,4 which is a promising topic for C



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The PXRD data were collected with a scan speed of 2°·min−1. The PXRD pattern at 100 °C is very similar to the roomtemperature one (25 °C), while the patterns at 200, 300, and 400 °C are very similar (Figure 6). The slight difference

Figure 4. The CIE chromaticity diagram of the complexes excited at 376 nm. A−E(Gd,Tb,Eu%): A(97,2,1), B(97.5,1.5,1), C(98,1,1), D(98.5,0.5,1), and E(99,0.5,0.5). Figure 6. PXRD patterns of complex 2 at different temperatures.

preparation of doping Ln(III) complexes used in light-emitting devices. However, when excited at 350 nm, no band centered at 440 nm was observed, and the emission color locates at the yellow-light region (CIE (0.480, 0.345)), which indicates that the energy transfer from the ligands to Eu(III)/Tb(III) ions in the doped complexes is very efficient. Therefore, we provide an approach to explore tunable white-light luminescence of LnCPs. Thermogravimetry (TGA) and Temperature-Dependent Powder X-ray Diffraction (PXRD). TGA and PXRD techniques were used to investigate the thermal stability of the chain structure. Complexes 1−3 exhibit similar thermal behavior (Figure 5 and Figure S5, Supporting Information);

between PXRD patterns at 200 and 100 °C at small angle is due to the removal of uncoordinated water molecules. Some diffraction peaks for the dehydrated sample shift to larger 2θ value because of lattice contraction, and small changes in intensity occur accordingly. However, the PXRD pattern at 500 °C is clearly different. So, the PXRD patterns indicate that after the removal of free water molecules, the 1D structure remains unchanged. The TGA and PXRD data show that the structural skeleton remains stable up to 400 °C, indicating the high stability of the dehydrated complex. And the dehydrated Eu(III)/Tb(III) complexes still show their characteristic luminescence (Figure S6, Supporting Information). To the best of our knowledge, LnCPs with thermal stability higher than 400 °C were rarely reported.11 The title complexes are highly thermostable lanthanide coordination polymers.

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CONCLUSIONS In summary, by use of H2bidc with phen ligand, novel 1D lanthanide coordination polymers {[Ln3(bidc)4(phen)2(NO3)]·2H2O}n (Ln = Gd (1), Eu (2), and Tb (3)) were obtained. They have the following features: (i) Their crystals are rare chain structures based on trinuclear units. (ii) The dehydrated complexes (latter water was removed) are stable up to 400 °C, showing high thermostability. (iii) Eu(III)/Tb(III) complexes show their characteristic fluorescence. And 1, 2, and 3 as blue-, red-, and greenlight-emitting components are incorporated into the resulting white-light-emitting materials by changing the relative amount of Gd(III), Eu(III), and Tb(III) in the doped complexes. Such doped lanthanide complexes can be a strategy for obtaining white-emitting materials.

Figure 5. The TGA curve of complex 2.

herein only 2 will be discussed in detail. The TGA of 2 shows that lattice water molecules can be removed at around 166 °C (the observed weight loss of 2.08%, calcd 2.29%), and the complex was stable up to around 410 °C. Above 410 °C, the TG curve exhibits second step of weight loss, which indicates decomposition of the organic ligands. And final product of 2 was Eu2O3 (the observed weight loss of 68.44%, calcd 69.50%).

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ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic files in CIF format, selected bond distances and bond angles and H-bonds for 1−3, PXRD D



Article

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patterns for complexes 1−3 and the doped complex, coordination modes of bidc ligand in complexes 1−3, 3D supramolecular structure of 2, excitation spectra and emission spectra of the ligands, decay profiles of complexes 1−3, excitation and emission spectra of the dehydrated complexes 1−3, TGA curves of complexes 2 and 3 and the doped complex, and CIE chromaticity coordinates for the doped complexes. This material is available free of charge via the Internet at http://pubs.acs.org. CCDC complexes 1 (CCDC862959), 2 (CCDC-855452), and 3 (CCDC-855454) contain the supplementary crystallographic data for this paper.

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +86 10 68902320. Fax: +86 10 68902320. E-mail: xiali@ mail.cnu.edu.cn. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful to the National Natural Science Foundation of China (Grant 21071101). REFERENCES

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Highly Thermostable One-Dimensional Lanthanide(III) Coordination

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