Temperature-Dependent Structures of Lanthanide Metal–Organic

May 12, 2012 - Hao Wang, Sui-Jun Liu, Dan Tian, Ji-Min Jia, and Tong-Liang Hu*. Department of Chemistry, TKL of Metal- and Molecule-Based Material ...
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Temperature-Dependent Structures of Lanthanide Metal−Organic Frameworks Based on Furan-2,5-Dicarboxylate and Oxalate Hao Wang, Sui-Jun Liu, Dan Tian, Ji-Min Jia, and Tong-Liang Hu* Department of Chemistry, TKL of Metal- and Molecule-Based Material Chemistry, and Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, P. R. China. S Supporting Information *

ABSTRACT: Two series of lanthanide metal−organic frameworks, [Ln(FDA)(OX)0.5(H2O)2]·(H2O) (1Ln) (Ln = Pr 1, Nd 2, Eu 3, Gd 4, Tb 5), [Ln(FDA)(OX)0.5(H2O)2]·(H2O) (2Ln) (Ln = Sm 6, Tb 7, Dy 8, Ho 9, Yb 10) (OX = oxalate), have been prepared by reacting Ln(NO3)3·6H2O with furan-2,5-dicarboxylic acid (H2FDA) at different temperatures under hydrothermal conditions. All the complexes are characterized by elemental analysis, IR, X-ray powder diffraction, and single-crystal X-ray diffraction. Structure analyses show that 1Ln and 2Ln are supramolecular isomerisms. 1Ln possesses a three-dimensional network with monoclinic space group P21/c, whereas 2Ln exhibits a three-dimensional framework with monoclinic space group C2/c. The distinct architectures of these two series of ten complexes indicated that the reaction temperature plays an important role in the formation of such coordination structures. Meanwhile, the photoluminescent properties of 4, 5, 7, and 8 are also investigated in the solid state at room temperature.

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INTRODUCTION The design and synthesis of novel metal−organic frameworks (MOFs) with desired properties are currently of great interest due to their potential application in catalysis,1 gas storage and separation,2 magnetism,3 fluorescence,4 proton conductivity,5 ferroelectric materials, and so on.6 Compared to d-block MOFs, which were studied widely, it is more difficult to rationally design lanthanide (Ln) MOFs, that is ascribed to the high coordination number and more flexible coordination geometry of Ln ions.7 However, Ln-MOFs have their unique special luminescent properties arising from the f electrons.8 Thus, to rationally design and construct Ln-MOFs is still a great challenge for taking advantage of the f electrons, as many factors can impact the overall structural formation. Except for the choice of ligands, reacting conditions, such as solvents, counteranions, the pH values of the reaction solutions, temperature, and molar ratio between reactants can also affect the final structure.9 So the investigation on the relationship between reacting conditions and the final structure can help us clearly know which reaction conditions lead to the desired structures. As it is known, Ln ions have high affinity and prefer to hard donor atoms, so ligands containing oxygen or combination of oxygen and nitrogen atoms, especially polycarboyxlate ligands, are used in the architecture for Ln-based MOFs.10 With regard to this matter, the furan-2,5-dicarboxylic acid (H2FDA) appears to be an appropriate candidate to construct Ln-based MOFs. H2FDA has two carboxylate groups with a “V-shaped” © 2012 American Chemical Society

configuration, which can form a variety of coordination polymers although a few compounds have been reported so far.11 On the other hand, our experimental work with this ligand under hydrothermal conditions has revealed that its in situ partial decomposition generates OX (OX = oxalate) anions, which can be introduced as a coligand. The cooperativity of both ligands can lead to the formation of unforeseen Ln-based MOFs.12 In this contribution, we report the syntheses, crystal structures and photoluminescent properties of nine Ln-based MOFs with the same formula, [Ln(FDA)(OX)0.5(H2O)2]·(H2O) (1Ln) (Ln = Pr 1, Nd 2, Eu 3, Gd 4, Tb 5), and [Ln(FDA)(OX)0.5(H2O)2]·(H2O) (2Ln) (Ln = Sm 6, Tb 7, Dy 8, Ho 9, Yb 10), which are supramolecular isomerisms due to the different reaction temperatures.

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EXPERIMENTAL SECTION

Materials and Physical Measurements. All chemicals including furan-2,5-dicarboxylic acid (H2FDA) used for synthesis were of analytical grade and commercially available. Elemental analyses (C and H) were performed on a Perkin-Elemer240C analyzer. IR spectra were measured on a Tensor 27 OPUS (Bruker) FT-IR spectrometer with KBr pellets. The luminescence spectra for the powdered solid samples were measured on a Varian Cary Eclipse fluorescence spectrophotometer, and all the measurements were carried out under the same Received: March 27, 2012 Revised: May 9, 2012 Published: May 12, 2012 3263

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Table 1. Crystal Data and Structure Refinement Parameters for Complexes 1−10

a

1

2

3

4

5

empirical formula formula weight temperature (K) crystal system space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z Dc (g·cm−3) F(000) θ range (deg) reflns collected independent reflns goodness-of-fit R1a (I > 2σ (I)) R2b (I > 2σ (I))

C7H8O10Pr 393.04 293(2) monoclinic P21/c 7.4786(15) 9.832(2) 15.487(5) 108.31(3) 1081.1(5) 4 2.415 756 3.30−25.20 9264 1938 1.010 0.0274 0.0538 6

C7H8O10Nd 396.37 293(2) monoclinic P21/c 7.4128(15) 9.771(2) 15.395(5) 108.33(3) 1058.5(5) 4 2.487 760 3.33−25.20 9096 1904 1.006 0.0287 0.0499 7

C7H8O10Eu 404.09 293(2) monoclinic P21/c 7.3519(15) 9.7295(19) 15.355(5) 108.54(3) 1041.3(4) 4 2.577 772 3.34−25.18 8929 1870 1.029 0.0240 0.0589 8

C7H8O10Gd 409.38 293(2) monoclinic P21/c 7.3173(15) 9.7022(19) 15.306(5) 108.61(3) 1029.8(4) 4 2.640 776 3.35−25.20 8901 1854 1.014 0.0257 0.0490 9

C7H8O10Tb 411.05 293(2) monoclinic P21/c 7.3108(15) 9.7220(19) 15.298(5) 108.75(3) 1029.6(4) 4 2.652 780 3.35−25.20 8896 1855 1.006 0.0200 0.0513 10

empirical formula formula weight temperature (K) crystal system space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z Dc (g·cm−3) F(000) θ range (deg) reflns collected independent reflns goodness-of-fit R1a (I > 2σ (I)) R2b (I > 2σ (I))

C7H8O10Sm 402.48 293(2) monoclinic C2/c 16.840(3) 10.608(2) 13.713(3) 117.11(3) 2180.4(8) 8 2.452 1536 3.20−25.18 9280 1956 1.011 0.0317 0.0541

C7H8O10Tb 411.06 293(2) monoclinic C2/c 16.775(3) 10.569(2) 13.697(3) 117.53(3) 2153.4(7) 8 2.536 1560 3.20−25.19 9284 1930 1.000 0.0260 0.0507

C7H8O10Dy 414.63 293(2) monoclinic C2/c 16.727(3) 10.537(2) 13.656(3) 117.62(3) 2132.5(7) 8 2.583 1568 3.21−25.20 9213 1917 1.014 0.0262 0.0594

C7H8O10Ho 417.06 293(2) monoclinic C2/c 16.677(3) 10.504(2) 13.640(3) 117.78(3) 2114.1(7) 8 2.621 1576 3.21−25.20 9105 1902 1.013 0.0251 0.0616

C7H8O10Yb 425.17 293(2) monoclinic C2/c 16.619(3) 10.460(2) 13.657(3) 118.13(3) 2093.6(7) 8 2.698 1600 3.21−25.20 9068 1884 1.006 0.0242 0.0520

R1 = Σ||Fo| − |Fc||/Σ|Fo|. bR2 = [Σ[w(Fo2 − Fc2)2]/Σw(Fo2)2]1/2. instead of Pr(NO3)3·6H2O. Light-purple prismatic crystals were obtained (yield = 25% based on Nd). FT-IR (KBr pellets, cm−1): 3132 s, 1560 m, 1400 s, 1047 w, 953 w, 783 w, 522 w. Anal. Calcd for C7H8O10Nd: C, 21.19; H, 2.02%. Found: C, 21.26; H, 2.15%. [Eu(FDA)(OX)0.5(H2O)2]·(H2O) (3). This compound was synthesized by a procedure similar to that of 1 except with Eu(NO3)3·6H2O instead of Pr(NO3)3·6H2O. Colorless prismatic crystals were obtained (yield = 18% based on Eu). FT-IR (KBr pellets, cm−1): 3133 s, 1568 m, 1400 s, 1024 w, 968 w, 783 w, 524 w. Anal. Calcd for C7H8O10Eu: C, 20.79; H, 1.98%. Found: C, 21.63; H, 2.14%. [Gd(FDA)(OX)0.5(H2O)2]·(H2O) (4). This compound was synthesized by a procedure similar to that of 1 except with Gd(NO3)3·6H2O instead of Pr(NO3)3·6H2O. Colorless prismatic crystals were obtained (yield = 20% based on Gd). FT-IR (KBr pellets, cm−1): 3132 s, 1558 m, 1400 s, 1044 w, 954 w, 575 w. Anal. Calcd for C7H8O10Gd: C, 20.52; H, 1.95%. Found: C, 20.69; H, 2.04%. [Tb(FDA)(OX)0.5(H2O)2]·(H2O) (5). This compound was synthesized by a procedure similar to that of 1 except with Tb(NO3)3·6H2O instead of Eu(NO3)3·6H2O. Colorless prismatic crystals were obtained (yield = 28% based on Tb). FT-IR (KBr pellets, cm−1): 3133 s, 1568

experimental conditions. Thermogravimetric (TG) analyses were carried out on a Rigaku standard TG-DTA analyzer with a heating rate of 10 °C min−1 from ambient temperature to 700 °C, an empty Al2O3 crucible was used as reference. The X-ray powder diffraction spectra (XRPD) were recorded on a Rigaku D/Max-2500 diffractometer at 40 kV, 100 mA for a Cu-target tube and a graphite monochromator. Simulation of the XRPD pattern was carried out by the single-crystal data and diffraction-crystal module of the Mercury (Hg) program version 1.4.2.13 Syntheses. Single crystals of complexes 1−10 suitable for X-ray analysis are obtained by the similar method, so only the synthesis of 1 is described in detail. [Pr(FDA)(OX)0.5(H2O)2]·(H2O) (1). A mixture of Pr(NO3)3·6H2O (0.087 g, 0.2 mmol), H2FDA (0.031 g, 0.2 mmol) and H2O (5 mL) was sealed in a 15 mL Teflon-lined autoclave at 180 °C for 2 days and then cooled to room temperature in 48 h. Light-green prismatic crystals were obtained (yield = 22% based on Pr). FT-IR (KBr pellets, cm−1): 3131 s, 1633 w, 1401 s, 1047 w, 953 w, 574 w. Anal. Calcd for C7H8O10Pr: C, 21.37; H, 2.03%. Found: C, 21.48; H, 2.12%. [Nd(FDA)(OX)0.5(H2O)2]·(H2O) (2). This compound was synthesized by a procedure similar to that of 1, except with Nd(NO3)3·6H2O 3264

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Figure 1. (a) Coordination mode of Tb3+ ion in 5, uncoordinated solvent molecules are omited for clarity (symmetry A x, −1 + y, z; B 1 − x, −0.5 + y, 1.5 − z; C −x, 1 − y, 1 − z; D 1 − x, 1 − y, 1 − z). (b) The coordination polyhedron of Tb3+ ion. (c) The 2D sheet of 5, the axial OX are omitted for clarity (symmetry A −x, 1 − y, 1 − z; B 1 − x, 0.5 + y, 1.5 − z; C 1 − x, −0.5 + y, 1.5 − z). (d) The 3D framework constructed via the pillar OX strutting the sheet, the coordinated water molecules are omitted for clarity. instead of Sm(NO3)3·6H2O. Colorless block crystals were obtained (yield = 32% based on Ho). FT-IR (KBr pellets, cm−1): 3133 s, 1577 m, 1400 s, 1047 w, 953 w, 800 w, 611 w. Anal. Calcd for C7H8O10Ho: C, 20.14; H, 1.92%. Found: C, 20.02; H, 1.82%. [Yb(FDA)(OX)0.5(H2O)2]·(H2O) (10). This compound was synthesized by a procedure similar to that of 6 except with Yb(NO3)3·6H2O instead of Sm(NO3)3·6H2O. Colorless block crystals were obtained (yield = 35% based on Yb). FT-IR (KBr pellets, cm−1): 3133 s, 1586 m, 1400 s, 1047 w, 953 w, 801 w, 613 w. Anal. Calcd for C7H8O10Yb: C, 19.76; H, 1.88%. Found: C, 19.83; H, 1.80%. X-ray Data Collection and Structure Determinations. X-ray single-crystal diffraction data for complexes 1−10 were collected on a Rigaku SCX-mini diffractometer at 293(2) K with Mo−Kα radiation (λ = 0.71073 Å) by ω scan mode. The program SAINT14 was used for integration of the diffraction profiles. All the structures were solved by direct methods using the SHELXS program of the SHELXTL package and refined by full-matrix least-squares methods with SHELXL (semiempirical absorption corrections were applied using SADABS program).15 Metal atoms in each complex were located from the Emaps and other non-hydrogen atoms were located in successive difference Fourier syntheses and refined with anisotropic thermal parameters on F2. The hydrogen atoms of the ligands were generated theoretically onto the specific atoms and refined isotropically with

m, 1401 s, 1047 w, 953 w, 783 w, 580 w. Anal. Calcd for C7H8O10Tb: C, 20.43; H, 1.95%. Found: C, 20.51; H, 1.81%. [Sm(FDA)(OX)0.5(H2O)2]·(H2O) (6). A mixture of Sm(NO3)3·6H2O (0.088 g, 0.2 mmol), H2FDA (0.031 g, 0.2 mmol) and H2O (5 mL) was sealed in a 15 mL Teflon-lined autoclave at 160 °C for 2 days and then cooled to room temperature in 48 h. Colorless block crystals were obtained (yield = 27% based on Sm). FT-IR (KBr pellets, cm−1): 3132 s, 1585 m, 1400 s, 1047 w, 954 w, 802 w, 613 w. Anal. Calcd for C7H8O10Sm: C, 20.89; H, 1.99%. Found: C, 20.71; H, 1.91%. [Tb(FDA)(OX)0.5(H2O)2]·(H2O) (7). This compound was synthesized by a procedure similar to that of 6 except with Tb(NO3)3·6H2O instead of Sm(NO3)3·6H2O. Colorless block crystals were obtained (yield = 28% based on Tb). FT-IR (KBr pellets, cm−1): 3131 s, 1586 m, 1400 s, 1047 w, 953 w, 801 w, 613 w. Anal. Calcd for C7H8O10Tb: C, 20.43; H, 1.95%. Found: C, 20.51 ; H, 1.84%. [Dy(FDA)(OX)0.5(H2O)2]·(H2O) (8). This compound was synthesized by a procedure similar to that of 6 except with Dy(NO3)3·6H2O instead of Sm(NO3)3·6H2O. Colorless block crystals were obtained (yield = 30% based on Dy). FT-IR (KBr pellets, cm−1): 3132 s, 1576 m, 1400 s, 1047 w, 954 w, 800 w, 669 w. Anal. Calcd for C7H8O10Dy: C, 20.26; H, 1.93%. Found: C, 20.25; H, 1.85%. [Ho(FDA)(OX)0.5(H2O)2]·(H2O) (9). This compound was synthesized by a procedure similar to that of 6 except with Ho(NO3)3·6H2O 3265

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Figure 2. (a) Coordination mode of Tb3+ ion in 7, uncoordinated solvent molecules are omited for clarity (symmetry A 0.5 − x, 1.5 − y, 2 − z; B − x, y, 1.5 − z; C x, −1 + y, z; D −x, 1 − y, 2 − z). (b) The coordination polyhedron of Tb3+ ion. (c) The 2D sheet of 7 constructed by 1D chain (blue solid line for 1D Tb3+ chain), the coordinated water molecules and the axial OX are omitted for clarity (symmetry A −x, 1 − y, 2 − z; B −0.5 + x, 0.5 + y, z). (d) The 3D framework constructed via the pillar OX strutting the sheet, the coordinated water molecules are omitted for clarity. fixed thermal factors. However, the hydrogen atoms of the water molecules were added by difference Fourier maps and refined with constrained. Detailed crystallographic data are summarized in Table 1. The selected bond lengths and angles are given in Table S1 (Supporting Information).

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asymmetric unit of 5 contains one unique Tb3+ ion, one FDA2‑ ligand, one-half oxalate ligand, two coordinated and one guest water molecule. As shown in Figure 1a, the Tb atom is eightcoordinated with four carboxylate oxygen atoms from four FDA2‑, two carboxylate oxygen atoms from one oxalate acid, and two oxygen atoms from two coordinated water molecules. The coordination polyhedron of Tb3+ is a distorted bicapped trigonal prism (Figure 1b). The Tb−O bond lengths vary from 2.302(3) to 2.473(3) Å. Because of the effect of lanthanide contraction, the Pr−O bond lengths in 1, the Nd−O bond lengths in 2, the Eu−O bond lengths in 3, and the Gd−O bond lengths in 4 are slight longer than the correspongding Tb−O bond lengths in 5 (Table S1, Supporting Information). In 1, the FDA2− ligand adopts only a single μ4-(η1,η1)-(η1,η1) bis-bidentate coordination mode connecting four Tb3+ ions and the oxalate ligand links two Tb3+ ions adopting a single tetradentate μ2-η1,η1,η1,η1 coordination mode, which indicates the high cooperativity between the FDA2‑ and oxalate ligands.16 The Tb3+ ions coordinate with four FDA2‑ ligands through the carboxylate oxygen atoms to generate a two-dimensional (2D) sheet (Figure 1c). The distances of Tb1···Tb1A, Tb1···Tb1B, and Tb1···Tb1C bridged with O−C−O of the FDA2‑ ligands are 5.037(2), 6.167(1) and 6.167(1) Å. These sheets are further united through the oxalate ligands to form a 3D framework (Figure 1d). The oxalate ligands are used as “Pillar” of adjacent

RESULTS AND DISCUSSION

Syntheses. Prismatic-shaped crystals of 1Ln and blockshaped crystals of 2Ln are obtained by reacting Ln(NO3)3·6H2O and H2FDA in water at 180 and 160 °C under hydrothermal conditions, respectively. Complexes 1−10 are stable toward oxygen and moisture and almost insoluble in common organic solvent. The IR spectra of 1−10 show the strong vibrations appearing around 1586 and 1400 cm−1 correspond to the asymmetric and symmetric stretching vibrations of the carboxylate groups, respectively (Figure S1, Supporting Information). The experimental XRPD patterns of 1−5 correspond well with the simulated XRPD pattern of 1, indicating that 1−5 are isostructural, so are compounds 6−10 (Figure S2−S3, Supporting Information). Crystal Structures of [Ln(FDA)(OX)0.5(H2O)2]·(H2O) (1Ln) (Ln = Pr 1,Nd 2, Eu 3, Gd 4, Tb 5). Single-crystal Xray diffraction studies show that complexes 1−5 are isostructural and crystallize in the monoclinic space group P21/c. Thus only the structure of 5 is described in detail. The 3266

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Figure 3. (a) 2D sheet of 5. A, B, and C represent 8-membered ring, 16-membered ring and 12-membered ring, respectively(symmetry A −x, 1 − y, 1 − z; B 1 − x, 0.5 + y, 1.5 − z; C 1 − x, −0.5 + y, 1.5 − z). (b) 2D sheet of 7. A and B represent 8-membered ring and 16-membered ring(symmetry A −x, 1 − y, 2 − z; B −0.5 + x, 0.5 + y, z).

sheets to bridge two Tb3+ ions with Tb···Tb distance being 6.285(1) Å. Crystal Structures of [Ln(FDA)(OX)0.5(H2O)2]·(H2O) (2Ln) (Ln = Sm 6, Tb 7, Dy 8, Ho 9, Yb 10). Complexes 6−10 are isostructural and crystallize in the monoclinic space group C2/c. As a representative example, the crystal structure of 7 is described in detail. There are one unique Tb3+ ion, one FDA2− ligand, one-half oxalate ligand, two coordinated and one guest water molecule in the asymmetric unit of 7. As illustrated in Figure 2a, the Tb3+ ion is eight-coordinated with distorted bicapped trigonal prism geometry (Figure 2b): four OCOO− from four FDA2− ligands, two OCOO− from one oxalate ligand and two oxygen atoms from two coordinated water molecules. The Tb−O bond lengths are in the range of 2.303(3)− 2.452(4) Å. Because of the effect of lanthanide contraction, the corresponding Tb−O bonds in 7 are slight longer than the Dy−O bonds in 8, the Ho−O bonds in 9, the Yb−O bonds in 10, and slight shorter than the Sm−O bonds in 6 (Table S1, Supporting Information). In 7, the FDA2− ligand adopts only a single μ4-(η1,η1)-(η1,η1) bis-bidentate coordination mode connecting four Tb3+ ions and the oxalate ligand links two Tb3+ ions adopting a single tetradentate μ2-η1,η1,η1,η1 coordination mode. The Tb3+ ions are double-bridged by bidentate carboxylate groups of FDA2‑ ligands to create a one-dimensional (1D) infinite chain with the Tb1···Tb1A and Tb1A···TbB distances being 5.011(1) and 5.004(1) Å, respectively. These chains are further bridged by FDA2− to generate a 2D sheet along ab plane (Figure 2c), then through the oxalate ligands forming a 3D framework (Figure 2d). The oxalate ligands are also used as “Pillar” of adjacent sheets to bridge two Tb3+ ions with the Tb···Tb distance being 6.218(2) Å.

Temperature-Dependent Structures. From the above description of crystal structures, it can be found that 1Ln and 2Ln exhibit different structures due to the different reaction temperatures. Complexes 1−5 are produced at higher temperature (180 °C) while compounds 6−10 are generated at lower temperature (160 °C). As described above, 1Ln and 2Ln have a strong similar structure, that is, the central metals are both eight-coordinated and form the distorted bicapped trigonal prism geometries, the FDA2− ligands both adopted μ4-(η1,η1)(η1,η1) bis-bidentate coordination mode by connecting four central metal ions, the oxalate ligands both link two central metal ions adopting a single tetradentate μ2 -η 1 ,η 1 ,η 1 ,η 1 coordination mode, and the final structures are both 3D generated by OX as the pillar to hold up the layer. But there are still some differences in their structures. The biggest difference is that, in ab plane, there are three types of rings in the 1Ln including 8-membered ring (A), 12-membered ring (C) and 16-membered ring (B) (Figure 3a). However there are only two types of rings in the 2Ln including 8-membered ring (A) and 16-membered ring (B) (Figure 3b). Each Ln ion bridges three adjacent ions through four OCOO− of four FDA2− ligands to generate a “knot” in the 1Ln (Figure 3a). But in 2Ln, each Ln ion bridges two adjacent ions through four OCOO− of four FDA2‑ ligands to build an “8”-type (Figure 3b). The different aspects of two kinds of supramolecular isomerism are unique decided by the different reaction temperatures. At higher temperature, FDA2− ligand adopts two orientation to construct three types of rings and “knot” to bridge the adjacent three Ln ions in the ab plane, but at lower temperature, FDA2− ligand adopts one orientation to build two types rings and “8”-type to bridge the near two Ln ions in the ab plane. 3267

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Figure 4. Emission spectra of (a) 4, (b) 5, (c) 7, and (d) 8.

assigned to the transitions of 4F9/2 → 6H15/2, 4F9/2 → 6H13/2, 4 F9/2 → 6H11/2, respectively. But its relative intensity is extremely lower comparable with 4, 5, and 7. The luminescent emission intensity of Ln3+ relies on the efficiency of the energy transfer from the ligand to Ln3+.8a,c−e So it indicates that the Dy3+ luminescence is not efficiently sensitized by the FDA2− ligand.

Thermal Stabilities. The isostructural frameworks lead to the similar thermal decomposition processes, so we took complexes 4 and 7 as representative examples for thermogravimetric analysis (TG). As shown in Figure S4, Supporting Information, complex 4 is stable up to 128 °C and show a weight loss 13.56% below 358 °C, corresponding to the loss of one guest water molecule and two coordinated water molecules (calcd 13.36%). Complex 7 shows the similar thermal behavior. It is stable up to 112 °C and shows a weight loss of 13.12% below 351 °C, corresponding to the loss of one guest water molecule and two coordinated water molecules (calcd 13.02%). Photoluminescence Properties. The solid-state luminescent properties of complexes 4, 5, 7, and 8 are investigated at room temperature with excitation wavelength at 390, 355, 355, and 390 nm, respectively. The emission peaks at 594, 618, 698 nm of 4 correspond to the transitions from 5D0 → 7Fn (n = 1, 2, and 4) of Eu3+ ion (Figure 4a). The 5D0 → 7F2 is the hypersensitive, which is made up of a single intense peak, resulting 4 emits intense red luminescence. Complexes 5 and 7 have closely similar coordinated environments of Tb3+, so the luminescent properties have almost no difference between them. As shown in the Figure 4b and 4c, the emission peaks at 548, 587, and 621 nm for 5, and 549, 588, and 621 nm for 7. They are attributed to the characteristic emission of 5D4 → 7Fn (n = 5, 4, 3) transitions of Tb3+ ion. The 5D4 → 7F5 is the hypersensitive, resulting 5 and 7 emit intense green luminescence. The characteristic emission of Dy3+ ion in 8 is shown in Figure 4d. Three peaks at 487, 577, and 660 nm are

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CONCLUSION

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ASSOCIATED CONTENT

Ten new 3D lanthanide MOFs based on H2FDA have been successfully synthesized under hydrothermal conditions at different temperatures. 1Ln and 2Ln are isomers produced by themperature-dependent. Each Ln ions bridged three adjacent ions through four OCOO− of four FDA2− ligands to generate a knot in 1Ln. But in 2Ln, each Ln ions bridged two adjacent ions through four OCOO− of four FDA2− ligands to build an 8type. The results of luminescent measurements for complexes 4, 5, 7, and 8 indicate that the Eu3+ and the Tb3+ luminescence are more efficiently sensitized by the ligand than the Dy3+.

S Supporting Information *

X-ray crystallographic data for complexes 1−10 in CIF format, the selected bond distances and angles for complexes 1−10 (Table S1), the IR spectra of 1−10 (Figure S1), the simulated and experimental XRPD for 1−10 (Figure S2 and S3), and the 3268

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TGA curves of 4 and 7 (Figure S4). This information is available free of charge via the Internet at http://pubs.acs.org/.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: +86-22-23502458. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the 973 Program of China (2012CB821700), the NNSF of China (21031002 and 51073079), and NSF of Tianjin, China (10JCZDJC22100 and 11JCYBJC04100).

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