Lanthanide Coordination Polymers Constructed from Imidazole-4,5

Jun 12, 2012 - coordination polymers (CPs) have attracted increasing attention in material research due to their many superior functional properties a...
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Lanthanide Coordination Polymers Constructed from Imidazole-4,5Dicarboxylate and Sulfate: Syntheses, Structural Diversity, and Photoluminescent Properties Wen-Guan Lu,*,† Di-Chang Zhong,‡ Long Jiang,§ and Tong-Bu Lu*,§ †

Department of Chemistry, Shaoguan University, Shaoguan 512005, China Key Laboratory of Organo-Pharmaceutical Chemistry of Jiangxi Province, Key Laboratory of Jiangxi University for Functional Material Chemistry, and College of Chemistry & Chemical Engineering, Gannan Normal University, Ganzhou 341000, China § MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, and School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China ‡

S Supporting Information *

ABSTRACT: Three series of lanthanide coordination polymers of {[Ln2(HIDC)2(SO4)(H2O)5]·H2O}n (CPs-1Ln, Ln = Sm, Eu, Tb, Dy, Ho, Er, and Yb), {(H2prz)[Ln2(HIDC)2(SO4)2]}n (CPs-2Ln, Ln = Sm and Eu), and [Ln2(HIDC)2(SO4)(H2O)2]n (CPs-3Ln, Ln = Tb, Dy, Ho, Er, and Yb) have been hydrothermally synthesized by the reactions of Ln(NO3)3·6H2O with imidazole-4,5-dicarboxylic acid (H3IDC) and sulfuric acid (H2SO4) in the presence of piperazine (prz) at different temperatures. The results of the single-crystal X-ray diffraction analysis reveal that CPs-1Ln presents a three-dimensional (3D) architecture, in which alternating one-dimensional (1D) right-/ left-handed helical chains of [Ln2(HIDC)2]∞ are interlinked by μ3SO42− anions. CPs-2Ln assumes a H2prz2+ templated 3D anionic layerpillared metal−organic framework (MOF) of {[Ln2(HIDC)2(SO4)2]}n2n−, in which two-dimensional (2D) (6,3) network layers of [Ln2(HIDC)2]n2n+ are pillared by μ2-SO42− anions. CPs-3Ln is a 2D layer structure, in which two 2D (6,3) monolayers of [Ln2(HIDC)2(H2O)2]n2n+ are connected by μ2-SO42− anions to form a 2D double-layer structure. The adjacent 2D double-layers are further stacked together via strong hydrogen bonding interactions to generate a 3D supramolecular framework. In addition, the results of photoluminescent measurements for Sm (1Sm and 2Sm), Eu (1Eu and 2Eu), Tb (1Tb and 3Tb), and Dy (1Dy and 3Dy) compounds in the solid state at room temperature indicate that different structural types have a different influence on their characteristic photoluminescences.

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INTRODUCTION In the past decade, the design and synthesis of lanthanide coordination polymers (CPs) have attracted increasing attention in material research due to their many superior functional properties and actual or potential applications.1−4 It is well-known that lanthanide ions have very high affinity and prefer to bind to hard donor atoms; thus nitrogen-containing heterocyclic carboxylic acids multidentate ligands, such as pyridine-,3c,5 pyrazole-,6 and imidazole-carboxylic acids,3e,7,8 etc., have been widely used in the construction of lanthanide coordination polymers. In comparison with transition metal ions, the lanthanide ions possess higher coordination numbers and more flexible coordination geometries, and thus lead to the formation of coordination polymers with versatile motifs.5f,9 In addition, lanthanide contraction may also influence the coordination numbers and generate diverse structures.6,7e,f,10 Therefore, to rationally design and construct lanthanide coordination polymers with desired geometries is still a challenge. © 2012 American Chemical Society

Imidazole-4,5-dicarboxylic acid (H3IDC), endowed with two carboxylate groups and a imidazole ring, is a versatile rigid ligand for the construction of coordination polymers. The carboxylate groups and imidazole ring could be partially or fully deprotonated at different pH values, which makes H3IDC possess diverse coordination modes. During the past few years, we and others have constructed a number of functional coordination polymers using metal ions and H3IDC as building blocks.3e,7,11−14 Very recently, we also found H3IDC can react with lanthanide ions in the presence of oxalic acid (H2OX) under weak basic conditions (pH = 8) to generate threedimensional (3D) lanthanide coordination polymers of {K5[Ln5(IDC)4(OX)4]·20H2O}n (Ln = Gd, Tb, and Dy), in which H3IDC is fully deprontonated.3e However, under weak acidic conditions (pH = 6), H3IDC is partially deprotonated to Received: April 8, 2012 Revised: June 3, 2012 Published: June 12, 2012 3675

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yield: 0.176 g, 42% based on Ho(NO3)3·6H2O. Anal. Calcd for C10H16Ho2N4O18S: C, 14.26; H, 1.91; N, 6.65%. Found: C, 14.32; H, 1.98; N, 6.56%. IR (KBr pellet, ν/cm−1): 3385 (s), 1661 (vs), 1611 (m), 1463 (w), 1438 (m), 1312 (w), 1235 (s), 1095 (s), 1050 (s), 986 (s), 955 (m), 640 (m), 596 (m), 562 (s). 1Er, pink crystals, yield: 0.150 g, 35% based on Er(NO 3 ) 3 ·6H 2 O. Anal. Calcd for C10H16Er2N4O18S: C, 14.18; H, 1.90; N, 6.62%. Found: C, 14.26; H, 1.93; N, 6.56%. IR (KBr pellet, ν/cm−1): 3379 (s), 1659 (vs), 1612 (m), 1463 (w), 1439 (m), 1315 (w), 1234 (s), 1095 (s), 1049 (s), 985 (s), 956 (m), 642 (m), 596 (m), 560 (s). 1Yb, colorless crystals, yield: 0.175 g, 41% based on Yb(NO 3 ) 3 ·6H 2 O. Anal. Calcd for C10H16Yb2N4O18S: C, 13.99; H, 1.88; N, 6.53%. Found: C, 14.06; H, 1.95; N, 6.50%. IR (KBr, cm−1): 3384 (s), 1660 (vs), 1612 (m), 1462 (w), 1440 (m), 1313 (w), 1233 (s), 1097 (s), 1051 (s), 985 (s), 957 (m), 641 (m), 596 (m), 559 (s). {(H2prz)[Ln2(HIDC)2(SO4)2]}n (CPs-2Ln, Ln = Sm and Eu), and [Ln2(HIDC)2(SO4)(H2O)2]n (CPs-3Ln, Ln = Tb, Dy, Ho, Er, and Yb). These two series of CPs-2Ln and CPs-3Ln were prepared at 170 °C by a procedure analogous to that for CPs-1Ln. For 2Sm, incarnadine crystals, yield: 0.146 g, 33% based on Sm(NO3)3·6H2O. Anal. Calcd for C14H16Sm2N6O16S2: C, 18.91; H, 1.81; N, 9.45%. Found: C, 18.65; H, 2.00; N, 9.36%. IR (KBr pellet, ν/cm−1): 3450 (s), 3116 (s), 1610 (vs), 1556 (vs), 1498 (s), 1439 (m), 1387 (vs), 1242 (w), 1111 (s), 962 (w), 853 (m), 808 (m), 787 (m), 656 (m), 613 (m), 577 (w), 511 (m). 2Eu, colorless crystals, yield: 0.160 g, 36% based on Eu(NO3)3·6H2O. Anal. Calcd for C14H16Eu2N6O16S2: C, 18.84; H, 1.81; N, 9.42%. Found: C, 18.76; H, 1.98; N, 9.38%. IR (KBr pellet, ν/ cm−1): 3452 (s), 3114 (s), 1612 (vs), 1554 (vs), 1500 (s), 1437 (m), 1386 (vs), 1244 (w), 1108 (s), 962 (w), 851 (m), 811 (m), 789 (m), 658 (m), 611 (m), 576 (w), 514 (m). For 3Tb, colorless crystals, yield: 0.146 g, 39% based on Tb(NO3)3·6H2O. Anal. Calcd for C10H8Tb2N4O14S: C, 15.84; H, 1.06; N, 7.39%. Found: C, 16.03; H, 1.12; N, 7.32%. IR (KBr pellet, ν/cm−1): 3293 (s), 3122 (m), 1664 (s), 1601 (s), 1578 (vs), 1503 (s), 1421 (s), 1400 (s), 1248 (m), 1182 (s), 1099 (w), 964 (w), 872 (m), 816 (m), 783 (m), 721 (w), 675 (m), 649 (m), 604 (m), 538 (w). 3Dy, colorless crystals, yield: 0.170 g, 44% based on Dy(NO3)3·6H2O. Anal. Calcd for C10H8Dy2N4O14S: C, 15.70; H, 1.05; N, 7.32%. Found: C, 15.78; H, 1.12; N, 7.40%. IR (KBr pellet, ν/cm−1): 3291 (s), 3120 (m), 1661 (s), 1598 (s), 1577 (vs), 1501 (s), 1419 (s), 1401 (s), 1250 (m), 1182 (s), 1097 (w), 964 (w), 871 (m), 820 (m), 781 (m), 719 (w), 675 (m), 650 (m), 602 (m), 541 (w). 3Ho, light orange crystals, yield: 0.115 g, 30% based on Ho(NO3)3·6H2O. Anal. Calcd for C10H8Ho2N4O14S: C, 15.60; H, 1.05; N, 7.28%. Found: C, 15.67; H, 1.12; N, 7.19%. IR (KBr pellet, ν/ cm−1): 3288 (s), 3121 (m), 1667 (s), 1602 (s), 1581 (vs), 1501 (s), 1417 (s), 1403 (s), 1246 (m), 1180 (s), 1102 (w), 961 (w), 870 (m), 813 (m), 781 (m), 721 (w), 674 (m), 650 (m), 604 (m), 540 (w). 3Er, pink crystals, yield: 0.130 g, 33% based on Er(NO3)3·6H2O. Anal. Calcd for C10H8Er2N4O14S: C, 15.50; H, 1.04; N, 7.23%. Found: C, 15.50; H, 1.14; N, 7.13%. IR (KBr pellet, ν/cm−1): 3293 (s), 3122 (m), 1664 (s), 1601 (s), 1578 (vs), 1503 (s), 1421 (s), 1400 (s), 1248 (m), 1182 (s), 1099 (w), 964 (w), 872 (m), 816 (m), 783 (m), 721 (w), 675 (m), 649 (m), 604 (m), 538 (w). 3Yb, colorless crystals, yield: 0.123 g, 31% based on Yb(NO3)3·6H2O. Anal. Calcd for C10H8Yb2N4O14S: C, 15.27; H, 1.02; N, 7.12%. Found: C, 15.41; H, 1.12; N, 7.02%. IR (KBr pellet, ν/cm−1): 3291 (s), 3119 (m), 1664 (s), 1599 (s), 1577 (vs), 1499 (s), 1421 (s), 1401 (s), 1246 (m), 1185 (s), 1100 (w), 961 (w), 872 (m), 815 (m), 782 (m), 719 (w), 674 (m), 651 (m), 604 (m), 540 (w). Determination of Crystal Structures. Single-crystal data for CPs-1Ln, CPs-2Ln, and CPs-3Ln were collected on an Agilent CrysAlis CCD, Gemini S Ultra system with graphite monochromatic Mo Kα radiation (λ = 0.71073 Å) except for 1Yb, 3Ho, and 3Er. Empirical absorption corrections were applied using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Single-crystal data for 3Er were collected on a Bruker Smart 1000 CCD diffractometer with graphite monochromatic Mo Kα radiation (λ = 0.71073 Å), and the Empirical absorption corrections were applied using the SADABS program.16 But single-crystal data for 1Yb and 3Ho were not collected due to its poor crystal quality. All the structures

form three series of two-dimensional (2D) lanthanide coordination polymers, namely, {[Ln(HIDC)(OX)0.5(H2O)2]·H2O}n (Ln = Pr and Nd), {[Ln(HIDC)(OX)0.5(H2O)2]·H2O}n (Ln = Eu and Tb), and [Ln(HIDC)(OX)0.5(H2O)]n (Ln = Pr, Nd, Eu, and Tb).7e These results indicate that the reaction conditions including pH value and temperature, as well as lanthanide contraction, could well tune the structures of lanthanide coordination polymers. Continuing our research on lanthanide coordination polymers with H3IDC, we used sulfuric acid (H2SO4) instead of H2OX as an auxiliary ligand to construct novel H3IDC-based lanthanide coordination polymers. Compared with H2OX, H2SO4 has more varied coordination modes and is preferable to bond to lanthanide ions and thus may facilitate the formation of unforeseen extended structures.5a,6c,7b−d,8b,10e,15 In this paper, we report three series of lanthanide coordination polymers based on mixed ligands of H3IDC and H2SO4, namely, {[Ln2(HIDC)2(SO4)(H2O)5]·H2O}n (CPs-1Ln, Ln = Sm, Eu, Tb, Dy, Ho, Er, and Yb), {(H2prz)[Ln2(HIDC)2(SO4)2]}n (CPs-2Ln, Ln = Sm and Eu, prz = piperazine), and [Ln2(HIDC)2(SO4)(H2O)2]n (CPs-3Ln, Ln = Tb, Dy, Ho, Er, and Yb). Their syntheses, crystal structures, and photoluminescent properties are discussed in detail.

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EXPERIMENTAL SECTION

H3IDC was prepared from benzoimidazole in about 80% yield. All the other reagents of analytical grade were obtained from commercial sources and used without further purification. Elemental analyses (EA) were determined using an Elementar Vario EL elemental analyzer. The infrared spectra (IR) were recorded in the 4000−400 cm−1 region as KBr pellets with a Bruker EQUINOX 55 spectrometer. Thermogravimetric analysis (TGA) data were collected on a Netzsch TG-209 instrument under air atmosphere in the temperature range of 20−800 °C with a heating rate of 10 °C/min. The powder X-ray diffraction (PXRD) measurements were recorded on a Bruker D8 ADVANCE powder X-ray diffractometer (Cu Kα, 1.5418 Å). Photoluminescent spectra were measured using an Edinburgh FLS920 fluorescence spectrometer for the solid powder samples under ambient temperature. {[Ln2(HIDC)2(SO4)(H2O)5]·H2O}n (CPs-1Ln, Ln = Sm, Eu, Tb, Dy, Ho, Er, and Yb). A mixture of Ln(NO3)3·6H2O (0.50 mmol), H3IDC (0.117 g, 0.75 mmol), H2SO4 (0.1 M, 2.5 mL), prz (0.086 g, 1.0 mmol), and 7.5 mL of water was stirred at room temperature for 30 min and then transferred to a 25 mL Teflon-lined stainless steel vessel. The reaction mixture was heated at 120 °C for 3 days under autogenous pressure. After being cooled slowly to room temperature, flake-shaped crystals of 1Ln were obtained. For 1Sm, incarnadine crystals, yield: 0.183 g, 45% based on Sm(NO3)3·6H2O. Anal. Calcd for C10H16Sm2N4O18S: C, 14.77; H, 1.98; N, 6.89%. Found: C, 14.86; H, 2.02; N, 6.68%. IR (KBr pellet, ν/cm−1): 3386 (s), 1660 (vs), 1612 (m), 1462 (w), 1440 (m), 1315 (w), 1236 (s), 1094 (s), 1050 (s), 985 (s), 957 (m), 641 (m), 595 (m), 560 (s). 1Eu, colorless crystals, yield: 0.158 g, 39% based on Eu(NO 3 ) 3 ·6H 2 O. Anal. Calcd for C10H16Eu2N4O18S: C, 14.71; H, 1.98; N, 6.86%. Found: C, 14.92; H, 2.11; N, 6.76%. IR (KBr pellet, ν/cm−1): 3386 (s), 1658 (vs), 1609 (m), 1463 (w), 1440 (m), 1315 (w), 1233 (s), 1094 (s), 1051 (s), 986 (s), 957 (m), 642 (m), 597 (m), 558 (s). 1Tb, colorless crystals, yield: 0.171 g, 41% based on Tb(NO 3 ) 3 ·6H 2 O. Anal. Calcd for C10H16Tb2N4O18S: C, 14.47; H, 1.94; N, 6.75%. Found: C, 14.52; H, 1.98; N, 6.56%. IR (KBr pellet, ν/cm−1): 3379 (s), 1658 (vs), 1611 (m), 1464 (w), 1440 (m), 1314 (w), 1235 (s), 1096 (s), 1051 (s), 985 (s), 957 (m), 639 (m), 598 (m), 561 (s). 1Dy, colorless crystals, yield: 0.159 g, 38% based on Dy(NO 3 ) 3 ·6H 2 O. Anal. Calcd for C10H16Dy2N4O18S: C, 14.34; H, 1.93; N, 6.69%. Found: C, 14.41; H, 2.03; N, 6.56%. IR (KBr pellet, ν/cm−1): 3380 (s), 1661 (vs), 1612 (m), 1461 (w), 1441 (m), 1315 (w), 1233 (s), 1093 (s), 1052 (s), 984 (s), 956 (m), 641 (m), 597 (m), 559 (s). 1Ho, light orange crystals, 3676

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Table 1. The Crystallographic Data for CPs-1Ln, CPs-2Ln, and CPs-3Ln compound

1Sm

1Eu

1Tb

1Dy

1Ho

1Er

formula formula weight crystal system space group a (Å) b (Å) c (Å) β (°) V (Å3) Z Dc (g cm−3) μ (mm−1) collected/unique Rint GOF on F2 R1, wR2 [I > 2σ(I)] R1, wR2 (all data) compound

C10H16Sm2N4O18S 813.03 monoclinic P2(1)/c 6.4022(2) 21.3894(7) 14.1932(5) 93.172(3) 1940.63(11) 4 2.783 6.208 9875/4228 0.0364 0.998 0.0288, 0.0446 0.0424, 0.0480 2Sm

C10H16Eu2N4O18S 816.25 monoclinic P2(1)/c 6.45920(10) 21.4480(5) 14.2117(3) 93.261(2) 1965.66(7) 4 2.758 6.536 10563/4292 0.0360 1.029 0.0280, 0.0427 0.0407, 0.0464 2Eu

C10H16Tb2N4O18S 830.17 monoclinic P2(1)/c 6.4504(3) 21.3003(8) 14.1455(5) 93.347(4) 1940.21(13) 4 2.842 7.447 7747/4123 0.0533 1.039 0.0444, 0.0852 0.0609, 0.0965 3Tb

C10H16Dy2N4O18S 837.33 monoclinic P2(1)/c 6.4417(2) 21.2712(5) 14.1377(4) 93.272(2) 1934.03(9) 4 2.876 7.884 7954/4117 0.0358 1.035 0.0353, 0.0710 0.0489, 0.0803 3Dy

C10H16Ho2N4O18S 842.19 monoclinic P2(1)/c 6.4406(2) 21.1952(9) 14.1015(5) 93.350(3) 1921.70(12) 4 2.911 8.393 9217/4137 0.0409 1.058 0.0345, 0.0603 0.0499, 0.0683 3Er

C10H16Er2N4O18S 846.85 monoclinic P2(1)/c 6.44350(10) 21.1512(5) 14.0950(3) 93.268(2) 1917.85(7) 4 2.933 8.910 9786/4125 0.0419 1.040 0.0333, 0.0596 0.0491, 0.0674 3Yb

formula formula weight crystal system space group a (Å) b (Å) c (Å) β (°) V (Å3) Z Dc (g cm−3) μ (mm−1) collected/unique Rint GOF on F2 R1, wR2 [I>2σ(I)] R1, wR2 (all data)

C14H16Sm2N6O16S2 889.14 monoclinic P2(1)/c 6.5550(2) 13.3453(4) 12.6525(4) 101.999(3) 1082.64(6) 2 2.728 5.666 4630/2343 0.0285 1.024 0.0285, 0.0497 0.0414, 0.0538

C10H8Dy2N4O14S 765.26 monoclinic C2/c 21.3070(9) 6.6298(2) 13.0431(6) 106.857(5) 1763.31(12) 4 2.883 8.617 4395/1921 0.0453 1.027 0.0336, 0.0675 0.0476, 0.0733

C10H8Er2N4O14S 774.78 monoclinic C2/c 21.143(5) 6.5928(14) 12.948(3) 106.242(3) 1732.8(6) 4 2.970 9.830 4494/1884 0.0231 1.090 0.0326, 0.0827 0.0383, 0.0863

C10H8Yb2N4O14S 786.34 monoclinic C2/c 21.0206(10) 6.5588(4) 12.8661(6) 106.016(5) 1705.00(15) 4 3.063 11.117 4832/1843 0.0278 1.022 0.0198, 0.0424 0.0256, 0.0431

C14H16Eu2N6O16S2 892.36 monoclinic P2(1)/c 6.5432(3) 13.3204(5) 12.6867(5) 101.694(4) 1082.80(8) 2 2.737 6.035 6058/2356 0.0340 1.021 0.0253, 0.0476 0.0342, 0.0509

C10H8Tb2N4O14S 758.10 monoclinic C2/c 21.3716(8) 6.6466(3) 13.0805(6) 106.971(4) 1777.15(13) 4 2.833 8.100 4231/1928 0.0425 1.047 0.0334, 0.0565 0.0493, 0.0634

Scheme 1. Synthetic Routes of Coordination Polymers CPs-1Ln, CPs-2Ln, and CPs-3Ln

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were solved using the direct method, which yielded the positions of all non-hydrogen atoms. These were refined first isotropically and then anisotropically. All the hydrogen atoms of the ligands were placed in calculated positions with fixed isotropic thermal parameters and included in structure factor calculations in the final stage of full-matrix least-squares refinement. The hydrogen atoms of coordinated water molecules in CPs-1Ln and CPs-3Ln, and the hydrogen atoms of lattice water molecules in CPs-1Ln were located in the difference Fourier maps and refined isotropically. All calculations were performed using the SHELXTL-97 system of computer programs.17 Crystallographic data and structural refinements are summarized in Table 1, and the selected bond lengths are listed in Table S1 in the Supporting Information.

RESULTS AND DISCUSSION

Synthesis Chemistry. Three series of lanthanide coordination polymers of CPs-1Ln, CPs-2Ln, and CPs-3Ln were synthesized by the hydrothermal reactions of H3IDC and H2SO4 with Ln(NO3)3·6H2O (Ln = Sm, Eu, Tb, Dy, Ho, Er, and Yb) in the presence of prz at different temperatures. The synthetic routes are shown in Scheme 1, and the synthetic rules can be concluded as follows: (1) the pH values and molar ratio of reactants play important roles on the formation of the final products. CPs-1Ln, CPs-2Ln, and CPs-3Ln with high yields were obtained in the pH value of ca. 6.0 and with the molar ratio of 3:1:2. Once these two conditions were slightly changed, the yields were low or only unidentified precipitates were 3677

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Scheme 2. Coordination Modes of HIDC2− and SO42− Observed in CPs-1Ln, CPs-2Ln, and CPs-3Ln

isolated. Especially, in the absence of H2SO4, a series of different compounds of {[Ln2(IDC)2(H2O)3]·1.5H2O}n were formed.7a,h (2) With the pH value of ca. 6.0 and the molar ratio of 3:1:2, CPs-1Ln, CPs-2Ln, and CPs-3Ln with diverse structures were tuned by altering the reaction temperatures, which illustrates the temperature is also a key factor to the formation of the final products. (3) prz is a versatile molecule in supramolecular assembly of CPs-1Ln, CPs-2Ln, and CPs-3Ln. For CPs-1Ln and CPs-3Ln, prz serves as a deprotonated agent. For CPs-2Ln, prz not only acts as a deprotonated agent but also serves as an effective templated agent. CPs-1Ln, CPs-2Ln, and CPs-3Ln exhibit good stability under ambient conditions and are insoluble in water and common organic solvents. The results of PXRD measurements indicate that the peaks displayed in the measured PXRD patterns closely match those in the simulated patterns generated from single-crystal diffraction data, indicating single phases of CPs-1Ln, CPs-2Ln, and CPs-3Ln were formed (Figure S1, Supporting Information). The PXRD patterns between different series (CPs-1Ln and CPs-2Ln, CPs-1Ln and CPs-3Ln, as well as CPs-2Ln and CPs-3Ln) are obviously different, while these within the same series (CPs-1Ln, CPs2Ln, and CPs-3Ln) are identical, indicating that the compounds within CPs-1Ln, CPs-2Ln, and CPs-3Ln are isomorphous. Therefore, only the structures of 1Er, 2Sm, and 3Er are described in detail. Structure of {[Er2(HIDC)2(SO4)(H2O)5]·H2O}n (1Er). The result of single-crystal X-ray diffraction analysis reveals that 1Er crystallizes in the monoclinic system with a space group P21/c. In the asymmetrical unit, there are two crystallographically independent Er(III) ions, two μ2-HIDC2− ligands (Scheme 2a), one μ3-SO42− anion (Scheme 2c), five coordinated water molecules, and one lattice water molecule. As illustrated in Figure 1a,b, both Er(1) and Er(2) ions are eight-coordinated in a distorted square antiprismatic geometry. Er(1) are coordinated by one nitrogen and four oxygen atoms from two individual μ2-HIDC2− ligands, two oxygen atoms of two individual μ3-SO42− anions, and two coordinated water molecules, while Er(2) is bonded to one nitrogen and three oxygen atoms from two individual μ2-HIDC2− ligands, one oxygen atom of a μ3-SO42− anion, as well as three coordinated water molecules. The Er−O distances are in the range of 2.233(4)−2.419(4) Å, and the Er−N distances are 2.413(5) and 2.460(5) Å, which is in good agreement with the reported distances for other Er(III) complexes.5f,6b,7d,10d−f As the ionic radii decreasing from Sm(III) to Yb(III) in 1Ln, all the Ln−O and Ln−N distances (Table S1, Supporting Information) decrease due to the effect of lanthanide contraction.6,7e,f,10 In 1Er, the μ2-HIDC2− ligands bridge Er(1) and Er(2) to generate one-dimensional (1D) left-/right-handed helical chains of [Er2(HIDC)2]∞ which run along a crystallographic

Figure 1. (a) The coordination environment of Er(III) ions and bridging modes of μ2-HIDC2− and μ3-SO42− in 1Er. (b) The coordination polyhedra of Er(III) ions. (c, d) The achiral 2D sheet containing the alternating right-/left-handed helical chains bridged by μ3-SO42− anions along the ac plane and a axis, respectively (the coordinated water molecules were omitted for clarity). (e) The 3D framework constructed by interconnection of achiral 2D sheets with μ3-SO42− anions (the brown polyhedra represent SO42− tetrahedron, and the lattice and coordinated water molecules were omitted for clarity).

21 axis, with a pitch of 6.444 Å (the pitch could be defined as the distance of alternate Er(1) or Er(2) along the a axis) (Figure 1c,d). The adjacent 1D helical chains of [Er2(HIDC)2]∞ are connected by μ3-SO42− anions in an alternate array, generating a 2D layer in the ac plane (Figure 1c,d). The left-/right-handed helical chains coexist in each layer; thus every layer does not exhibit chirality. The achiral layers are further linked by μ3-SO42− anions along the a axis, 3678

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Figure 2. (a) The coordination environment of Sm(III) ion and bridging modes of μ3-HIDC2− and μ2-SO42− in 2Sm. (b) The coordination polyhedron of Sm(III) ion. (c, d) The 2D layer structure of [Sm2(HIDC)2]n2n+ along the ab plane and a axis, respectively. (e) The (6,3) topological network of 2D layer along the ab plane (the green and violet nodes in the network represent Sm(III) ions and the center of μ3-HIDC2− ligands, respectively). (f, g) The 3D anionic framework of [Sm2(HIDC)2(SO4)2]n2n−, showing two types of 1D channels of A and B along the a axis, channels of A are filled with H2prz2+ cations, which are shown as space-filling models. (h) Schematic representation of binodal (3,5)-connected topological net (color code: green ball, 5-connected Sm(III) node; violet ball, the center of 3-connected μ3-HIDC2− ligands; yellow stick, 2-connected μ2-SO42− anions).

channels B are obturated due to the imidazole rings point inward, no molecules locate in vacancies (Figure 2g). A topological method was performed to further analyze the anionic framework of 2Sm. The μ2-SO42− anions connecting two Sm(1) can be seen as linkers. Each μ3-HIDC2− ligand, linking three Sm(1), can be regarded as 3-connected nodes, and each Sm(1), connecting three μ3-HIDC2− ligands and two μ2SO42− anions, can be considered as a 5-connected node. Therefore, the anionic framework structure of 2Sm can be described as a binodal (3,5)-connected gra network with total Schläfli symbol of (63)(69·8) (Figure 2h). Structure of [Er2(HIDC)2(SO4)(H2O)2]n (3Er). The asymmetric unit in 3Er comprises one Er(III) ion, one μ3-HIDC2− ligand (Scheme 2b), half μ2-SO42− anion (Scheme 2d), and one coordinated water molecule O(1W). As shown in Figure 3a, the Er(1) coordinates to four oxygen atoms and one nitrogen atom from three individual μ3-HIDC2− ligands, one bis-chelating μ2SO42− anion, and one coordinated water molecule, resulting in an eight-coordinated distorted bicapped trigonal prism geometry (Figure 3b). In 3Ln, both Ln−O and Ln−N distances (Table S1, Supporting Information) decrease along with the increase lanthanide atomic numbers from Tb to Yb due to the lanthanide contraction.6,7e,f,10 In 3Er, the Er(1) ions are connected via μ3-HIDC2− ligands to form a 2D (6,3) cationic monolayer of [Er2(HIDC)2(H2O)2]n2n+ along the bc plane (Figure 3c,d,e). Two 2D monolayers are further pillared by μ2-SO42− anions to generate a 2D neutral double-layer of [Er2(HIDC)2(SO4)(H2O)2]n, in which all the coordinated water molecules point out of the 2D double-layer (Figure 3f). Through the interlayer hydrogen bonding interactions (Table S2, Supporting Information), the adjacent double-layers are further stacked

resulting in a 3D framework with 1D channels (Figure 1e). The lattice water molecules are suspended in the channels (Figure S2, Supporting Information), and the coordinated water molecules O(2W), O(4W), and O(5W) point to the channels. There are strong hydrogen bonding interactions among μ2HIDC2− ligands, μ3-SO42− anions, coordinated water molecules, as well as lattice water molecules (Table S2, Supporting Information). Structure of {(H2prz)[Sm2(HIDC)2(SO4)2]}n (2Sm). 2Sm crystallizes in the monolinic system with a space group of P21/c. The asymmetric unit comprises one Sm(III) ion, one μ3HIDC2− ligand (Scheme 2b), one μ2-SO42− anion (Scheme 2d), and half protonated prz cation (H2prz2+). As shown in Figure 2a, the Sm(1) is nine-coordinated with four oxygen atoms and one nitrogen atom from three individual μ3-HIDC2− ligands, and four oxygen atoms from two individual bischelating μ2-SO42− anions, resulting in a distorted tricapped trigonal prism (Figure 2b). Similar to 1Ln, both Ln−O and Ln−N distances in 2Ln (Table S1, Supporting Information) decrease from 2Sm to 2Eu due to the effect of lanthanide contraction. In 2Sm, each μ3-HIDC2− ligand connects three Sm(1) to form an undulated 2D (6,3) layer of [Sm2(HIDC)2]n2n+ along the ab plane (Figure 2c−e), which are further pillared by the μ2-SO42− anions to generate a 3D porous anionic framework of [Sm2(HIDC)2(SO4)2]n2n− (Figure 2f). There are two types of channels (A and B) with size of 6.8 × 6.3 Å along the a axis (measured by the Sm···Sm distances) (Figure 2f). The channels A are occupied by the protonated prz cations (H2prz2+) to balance the charge of the frameworks, in which there are strong hydrogen bonding interactions between H2prz2+ cations and framework (Table S2, Supporting Information). While the 3679

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Figure 3. (a) The coordination environment of Er(III) ion and bridging modes of μ3-HIDC2− and μ2-SO42− in 3Er. (b) The coordination polyhedron of Er(III) ion. (c, d) The 2D monolayer structure of [Er2(HIDC)2(H2O)2]n2n+ along the bc plane and b axis, respectively (the coordinated water molecules were omitted for clarity). (e) The (6,3) topological network of 2D monolayer along the bc plane (the green and violet nodes in the network represent Er(III) ions and the center of μ3-HIDC2− ligands, respectively). (f) The 2D double-layer architecture of [Er2(HIDC)2(SO4)(H2O)2]n. (g) The topological representation of the 2D double-layer structure (color code: green ball, 4-connected Er(III) node; violet ball, the center of 3-connected μ3-HIDC2− ligands; yellow stick, 2-connected μ2-SO42− anions). (h) The 3D supramolecular framework assembled via interlayer hydrogen bonding interactions between the 2D double-layer (hydrogen bonds shown as dashed lines).

Thermogravimetric Analysis. The stabilities of CPs-1Ln, CPs-2Ln, and CPs-3Ln were examined by thermogravimetric analyses (TGA) in air atmosphere from the temperature of 20− 800 °C. The results indicate that all the compounds within CPs-1Ln, CPs-2Ln, and CPs-3Ln show similar thermal behavior owing to their isomorphous structures; thus only the thermal stabilities of 1Er, 2Sm, and 3Er are discussed in detail (Figure 4). The TGA curve of 1Er shows the initial weight loss of 13.2% in the temperature range from 50 to 400 °C, corresponding to the release of one lattice water molecule and five coordinated water molecules per formula unit (calcd 12.8%). The framework begins to decompose upon further

together along the a axis, resulting in a 3D supramolecular framework of 3Er (Figure 3h). According to the regularity of the topological analysis method, each Er(1), connecting with three μ3-HIDC2− ligands and one μ2-SO42− anion, should be regarded as a 4-connected node. The μ3-HIDC2− and μ2-SO42− linking with three and two Er(III) ions, respectively, can be considered as 3-connected nodes and linkers, respectively. Thus, the network topology of 3Er can be best described as a novel 2D binodal (3,4)connected network with total Schläfli symbol of (63)(66) (Figure 3g). Structural Diversity. It is interesting to find that although all three series of lanthanide coordination polymers of CPs1Ln, CPs-2Ln, and CPs-3Ln are constructed by Ln(NO3)3 with HIDC2− ligand and SO42− anion under similar conditions, they exhibit different structural motifs. The diverse structures of CPs-2Ln and CPs-3Ln may be ascribed to lanthanide contraction. In CPs-2Ln, each Sm(III) or Eu(III) ions is nine-coordinated by three μ3-HIDC2− ligands and two μ2SO42− anions (Figure 2a,b), while in CPs-3Ln, the Tb(III)− Yb(III) ions with smaller ion radii can only be eightcoordinated by three μ3-HIDC2− ligands, one μ2-SO42− anion, and one water molecule (Figure 3a,b). The reaction temperature also plays an important role to the structural diversity, as it can affect the number of the coordinated water molecules.7e,18 CPs-1Ln, obtained at lower temperature, contain more coordinated water molecules than CPs-2Ln/ CPs-3Ln which were obtained at higher temperature. Similar results can be found in the literature.7e,18c,d

Figure 4. TGA curves for 1Er, 2Er, and 3Sm. 3680

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heating. The TGA curve of 2Sm shows its framework was stable up to 300 °C and began to decompose upon further heating. The TGA curve of 3Er shows a weight loss of 4.1% in the 50−300 °C temperature range, corresponding to the loss of the coordinated water molecule (4.6%). And then, the framework begins to decompose upon further heating. Luminescent Properties. Lanthanide coordination polymers are potential luminsescent materials as they often show narrow, sharp, and well-separated emission bands.1,3,4 As shown in Figure 5, excited at 402 nm, the emission spectra of 1Sm and 2Sm show three characteristic bands at 562, 597, and 642 nm (Figure 5a), respectively, which are attributed to the transitions from 4G5/2 to 6HJ (J = 5/2, 7/2, and 9/2) of Sm(III) ion,5c,h,6b,10f,19c,20 while the 4G5/2 → 6H11/2 transition was not observed. For 1Eu and 2Eu, when excited at 249 nm, they display strong red luminescence in the region of 580, 589−597, 612−619, 651, and 700 nm (Figure 5b), which can be assigned to the transitions of Eu(III) ion from 5D0 excited state to different 7FJ (J = 0−4) states,3−7,10f,19c,20 while the intensities of 5 F0 → 7F3 (651 nm) and 5F0 → 7F4 (700 nm) transitions are very weak and could hardly be observed (Figure 5b). When excited at 276 nm, 1Tb and 3Tb emit four characteristic bands of Tb(III) ion at 489, 544, 589, and 622 nm (Figure 5c), which are assigned to 5 D 4 → 7 F J (J = 6, 5, 4, and 3) transitions.3−7,10f,20 1Dy and 3Dy also display the typical emission of Dy(III) ion when excited at 350 nm. The emission bands at 479−488, and 573−576 nm can be attributed to the 4 F9/2 → 6HJ (J = 15/2 and 13/2) transitions of Dy(III) ion,5c,h,6b,10f,19c,20 while the 4F9/2 → 6H11/2 band was not observed (Figure 5d). Compared with Sm (1Sm and 2Sm) and Dy (1Dy and 3Dy) compounds, the luminescence emission of Eu (1Eu and 2Eu) and Tb (1Tb and 3Tb) compounds is easily detected under the same experimental conditions. This is also reflected in the luminescence emission decay measurements performed for these compounds (Figure S3, Supporting Information). The room temperature luminescence emission decay curves are characterized by a monoexponential function with the lifetime values of 1Sm and 2Sm for 4G5/2 → 6H7/2 transitions, 1Eu and 2Eu for 5F0→7F2 transitions, 1Tb and 3Tb for 5D4 → 7F5 transitions, 1Dy and 3Dy for 4F9/2 → 6H13/2 transitions are around 6.96, 7.32, 208.30, 224.15, 287.48, 589.46, 4.87, and 4.94 μs, respectively, which are similar to those reported values for Eu(III), Tb(III), Sm(III), and Dy(III) compounds.20 The luminescence emissions of Er (1Er and 3Er) and Yb (1Yb and 3Yb) compounds were too weak to be detected (not shown),19 probably due to the quenching effect of the N−H groups in HIDC2− ligands and O−H groups of coordinated water molecules.1,19−21 So the intensities of energy transitions from the ligands to lanthanide ions change in the order of Tb(III), Eu(III) > Sm(III), Dy(III) > Er(III), Yb(III), which may be because of the different energy gaps of various lanthanide ions.1b−f,19c,20,21 Making a comparison of luminescent properties between 1Sm and 2Sm, 1Eu and 2Eu, 1Tb and 3Tb, as well as 1Dy and 3Dy, it is noteworthy that CPs-2Ln/CPs-3Ln exhibit stronger emission intensities and slightly longer fluorescence lifetimes than CPs-1Ln, which can be attributed to their different structural motifs, just as revealed by single crystal structure analysis. Nevertheless, the difference in the structures produced little effects on the peaks position in the spectra. In general, the luminescence emission intensity of lanthanide coordination polymers is very dependent on the coordination environment

Figure 5. Emission spectra of (a) 1Sm and 2Sm, (b) 1Eu and 2Eu, (c) 1Tb and 3Tb, and (d) 1Dy and 3Dy in the solid state at room temperature.

of the lanthanide ions, which can influence the efficiency of the energy transfer from the ligand to lanthanide ions.1,3,4 It has also been demonstrated that the presence of lattice and coordinated water molecules in the structure is probably the main quenching route and can decrease the luminescence 3681

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Crystal Growth & Design emission intensity of lanthanide coordination polymers, as the thermal oscillation of water molecules will consume some excitation energy absorbed by “antenna” ligands.1,3,4,7e,20,21 There are one lattice and five coordinated water molecules in CPs-1Ln, while there is not or only one coordinated water molecule in CPs-2Ln/CPs-3Ln, respectively; thus the emission intensities of CPs-2Ln/CPs-3Ln are much stronger than those of CPs-1Ln due to less deactivation in CPs-2Ln/CPs-3Ln. In addition, the HIDC2− ligand adopts μ3-HIDC2− coordination mode (Scheme 2b) in CPs-2Ln/CPs-3Ln, while it adopts μ2HIDC2− coordination mode (Scheme 2a) in CPs-1Ln, and the μ3-HIDC2− coordination mode makes HIDC2− more rigid, which makes the energy transfer process from μ3-HIDC2− to lanthanide ions more effective in CPs-2Ln/CPs-3Ln.1,7e,21 Moreover, each lanthanide ion coordinates to two μ2-HIDC2− in CPs-1Ln ligands, while it coordinates to three μ3-HIDC2− ligands in CPs-2Ln/CPs-3Ln, respectively. Thus, this allows the lanthanide ions in CPs-2Ln/CPs-3Ln to absorb more light energy from more HIDC2− “antenna” ligands than in CPs1Ln.1,21b Therefore, CPs-2Ln/CPs-3Ln exhibit stronger emission intensities and slightly longer fluorescence lifetimes than CPs-1Ln, which are very consistent with the fact that the existence of the more rigidly coordinated μ3-HIDC2− ligand, as well as the lower number of coordinated water molecules in CPs-2Ln/CPs-3Ln.

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REFERENCES

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CONCLUSION In summary, by using prz as deprotonated or templated agent, three series of lanthanide coordination polymers of CPs-1Ln, CPs-2Ln, and CPs-3Ln with three different structural motifs have been successfully synthesized under hydrothermal conditions at different reacting temperatures. The influence of reaction conditions such as pH value, molar ratio, and temperature of the reaction system on the formation of final products and the polymeric architectures was investigated in detail. The results show that lower reaction temperature favors the formation of CPs-1Ln, and higher reaction temperature is beneficial for the formation of CPs-2Ln/CPs-3Ln. The successful isolation of CPs-1Ln, CPs-2Ln, and CPs-3Ln provides a good example of tuning structure by the reaction temperature and lanthanide contraction effect. The results of luminescent measurements for CPs-1Ln and CPs-2Ln/CPs3Ln indicate that the emission intensities of CPs-2Ln/CPs-3Ln are slightly stronger than those of CPs-1Ln, which are attributed to the existence of more rigid μ3-HIDC2− ligands, as well as lower numbers of water molecules in CPs-2Ln/CPs3Ln. ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic files in CIF format, tables listing selected bond distances, and PXRD patterns of CPs-1Ln, CPs-2Ln, and CPs-3Ln, luminescent decay curves for 1Sm, 2Sm, 1Eu, 2Eu, 1Tb, 3Tb, 1Dy, and 3Dy. This material is available free of charge via the Internet at http://pubs.acs.org.

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ACKNOWLEDGMENTS

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21071099 and 20831005).

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (W.G.L.); lutongbu@mail. sysu.edu.cn (T.B.L.). Notes

The authors declare no competing financial interest. 3682

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Crystal Growth & Design

Article

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dx.doi.org/10.1021/cg300476e | Cryst. Growth Des. 2012, 12, 3675−3683