Hydrothermal Syntheses, Crystal Structures, and Luminescence

Mar 29, 2015 - Universal V2.6 DTA system at a rate of 10 °C/min in a nitrogen atmosphere. ...... (f) Schematic view of the 2D sql net: the dimetallic...
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Hydrothermal Syntheses, Crystal Structures, and Luminescence Properties of Lanthanide-Based Coordination Polymers Constructed by Sulfonate Functionalized Imidazophenanthroline Derivative Ligand Bing Xu, Qing Chen, Huai-Ming Hu,* Ran An, Xiaofang Wang, and Ganglin Xue Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069, China S Supporting Information *

ABSTRACT: Ten new LnIII-H3sfpip compounds [Pr(Hsfpip)(fum)0.5(H2O)]n· n(H2O) (1), [Ln(Hsfpip)(glu)0.5(H2O)2]n·n(H2O) (Ln = La (2), Pr (3), Sm (4)), [Ln2(Hsfpip)2(OH)2(H2O)6]n·2n(H2O) (Ln = Dy (5), Ho (6), Er (7)), [La(Hsfpip)(adip)0.5(H2O)2]n (8), [Y(Hsfpip)(suc)0.5(H2O)3]n·n(H2O) (9), and [Y(Hsfpip)(adip)0.5(H2O)2]n·n(H2O) (10) (H2fum = fumaric acid, H2suc = succinic acid, H2glu = glutaric acid, H2adip = adipic acid, H3sfpip =2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compounds 1−4 possess 2D layered structures based on alternately arranged loop chains with fum2− anions and glu2− anions as bridges, respectively. Compounds 5−7 are isostructural and show 2D layered structures containing binuclear Ln2 units, while the hydroxyl groups participated in the construction of structures. Compound 8 is a 3D network built up by polygonal La2(COO)2 binuclear units. Compound 9 displays a 2D layer which is extended to a 3D supramolecular framework by means of weak interactions. Compound 10 presents a 3D network structure with (adip)2− anions as bridges. The versatile structures well exhibit the rich coordination chemistry of H3sfpip and the coordination geometries of LnIII ions. In addition, the photoluminescence and thermal stabilities of 1−10 were also studies.

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INTRODUCTION Unprecedented attention has been paid to the design and fabrication of coordination polymers stemming from their fascinating potential applications in catalysis, gas storage, separation, ion exchange, etc.1 However, compared with the splendid works based on transition metals, the chemistry of lanthanide remains less developed. Apart from transition metal centers, the lanthanide ions attract research interest worldwide mainly because of two reasons. First, they often demonstrate high and variable coordination numbers, as well as diverse coordination geometries, which can lead to versatile and amazing structures. Second, they are fascinating luminescent sources due to their high color purity and relatively long lifetimes arising from electronic transitions within the partially filled 4f shell of the ions, which make them potential candidates in fluorescent probes, light-emitting diodes, and conversion or amplification of light.2 Nevertheless, owing to the intrinsic uncontrollability of lanthanide metal ions, the rational design of lanthanide-based coordination polymers is more challenging than the design of coordination polymers with transition metal ions.3,4 Although lanthanide ions have excellent luminescence properties from visible to near-infrared regions,5 it has been well-known that direct excitation of lanthanide metal centers is © XXXX American Chemical Society

compromised by the inefficient absorption of light via f−f electronic transitions, which are formally Laporte forbidden.6 Thus, a sensitizer, often referred to as a “light harvester” or “antenna” molecule, is required within the local environment of the ion to harvest the absorption of photon energy and to enhance the efficiency of emission.7 In order to accomplish this purpose, judicious selection and synthesis of organic ligands have proved to be a feasible approach. Over the past decades, 1,10-phenanthroline (phen) and its derivatives have been widely used as not only chelating but also bridging ligands.8−15 We are also interested in constructing coordination polymers based on this kind of ligand and have already made some development in this field.16−20 Compared with the ligands used before, we unprecedentedly introduced sulfonic group into the reaction system. Afterward, we reported three lead coordination polymers derived from 2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline (H3sfpip, Scheme 1), as well as their luminescence and thermal properties.21 For the sake of enriching our research system and making the utmost use of its superiorities, H3sfpip is employed continuously to construct Received: January 27, 2015 Revised: March 26, 2015

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DOI: 10.1021/acs.cgd.5b00117 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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1198(s), 1076(s), 1035(s), 806(s), 739(s), 691(s), 641(s), 620(s), 516(s). 1H NMR data (400 MHz, DMSO): δ 9.15 (d, J = 7.9 Hz, 2H), 8.30 (dd, J = 39.4, 8.7 Hz, 2H), 7.87 (d, J = 7.4 Hz, 1H), 6.04(m, 4H). 13 C NMR data (101 MHz, DMSO): δ 156.06, 154.86, 150.82, 150.02, 140.62, 140.14, 136.06, 134.19, 131.70, 131.27, 130.05, 129.93, 126.98. HRMS(ESI): m/z [M + H]+ calcd for C19H12N4O6S2, 457.0277; found, 457.0268. Preparation of [Pr(Hsfpip)(fum)0.5(H2O)]n·n(H2O) (1). A mixture of Pr(NO3)3·6H2O (21.7 mg, 0.05 mmol), H3sfpip (22.8 mg, 0.05 mmol), and H2fum (11.6 mg, 0.1 mmol) in distilled water (12 mL) was stirred for 30 min in air, then sealed in a 25 mL Teflonlined stainless steel container, which was heated to 180 °C for 3 days, and then slowly cooled to room temperature at a rate of 5 °C/h. Light yellow strip-like crystals of 1 were obtained, yield: 23 mg, 65.6% based on Pr. Anal. Calcd (%) C21H11N4O11PrS2 (700.37): C 36.01; H 1.58; N 7.99%. Found: C 36.05; H 1.59; N 7.92%. IR (KBr, cm−1): 3528(w), 3448(m), 3091(w), 1641(w), 1559(s), 1449(m), 1406(s), 1248(w), 1219(m), 1172(s), 1081(s), 1037(s), 966(w), 867(w), 810(m), 732(m), 687(m), 642(s), 615 (s), 511(s). Preparation of [La(Hsfpip)(glu)0.5(H2O)2]n·n(H2O) (2). A mixture of La(NO3)3·6H2O (21.6 mg, 0.05 mmol), H3sfpip (22.8 mg, 0.05 mmol), and H2glu (13.2 mg, 0.1 mmol) in distilled water (12 mL) was stirred for 30 min in air, then sealed in a 25 mL Teflon-lined stainless steel container, which was heated to 180 °C for 3 days, and then slowly cooled to room temperature at a rate of 5 °C/h. Light yellow strip-like crystals of 2 were obtained, yield: 22.4 mg, 62.8% based on La. Anal. Calcd (%) for C21.50H19N4O11LaS2 (712.44): C 36.24; H 2.68; N 7.86%. Found: C 36.25; H 2.69; N 7.88%. IR (KBr, cm−1): 3443(s), 1614(s), 1515(m), 1452(m), 1429(s), 1335(m), 1250(s), 1164(s), 1297(w), 1129(m), 1081(s), 1031(m), 819(w), 738(m), 890(m), 837(m), 561(m), 515(s). Preparation of [Pr(Hsfpip)(glu)0.5(H2O)2]n·n(H2O) (3). Compound 3 was synthesized by a method similar to that of 2, except that La(NO3)3·6H2O was replaced by Pr(NO3)3·6H2O accordingly. Light yellow strip-like crystals of 3 were obtained, yield: 22.1 mg, 62% based on Pr. Anal. Calcd (%) for C21.50H19N4O11PrS2 (714.44): C 36.14; H 2.68; N 7.84%. Found: C 36.15; H 2.69; N 7.82%. IR (KBr, cm−1): 3423(s), 1642(m), 1520(m), 1452(w), 1430(s), 1335(w), 1250(s), 1164(s), 1129(w), 1081(m), 1031(s), 821(m), 738(m), 691(m), 638(s), 561(m), 516(m). Preparation of [Sm(Hsfpip)(glu)0.5(H2O)2]n·n(H2O) (4). Compound 4 was synthesized by a method similar to that of 2, except that Pr(NO3)3·6H2O was replaced by Sm(NO3)3·6H2O accordingly. Yellow strip-like crystals of 4 were obtained, yield: 18.7 mg, 51.8% based on Sm. Anal. Calcd (%) for C21.50H19N4O11SmS2 (721.86): C 35.67; H 2.64; N 7.74%. Found: C 35.65; H 2.69; N 7.72%. IR (KBr, cm−1): 3421(s), 1641(s), 1523(s), 1452(m), 1431(s), 1363(s), 1335(m), 1249(s), 1165(s), 1130(m), 1081(m), 1031(s), 845(w), 821(m), 738(s), 690(s), 638(s), 561(s),516 (m), 419(m). Preparation of [Dy2(Hsfpip)2(OH)2(H2O)6]n·2n(H2O) (5). A mixture of Dy(NO3)3·6H2O (22.8 mg, 0.05 mmol), H3sfpip (22.8 mg, 0.05 mmol), and H2suc (11.8 mg, 0.1 mmol) in distilled water (12 mL) was stirred for 30 min in air, then sealed in a 25 mL Teflon-lined stainless steel container, which was heated to 180 °C for 3 days, and then slowly cooled to room temperature at a rate of 5 °C/h. Yellow block crystals of 5 were obtained, yield: 12.7 mg, 36.8% based on Dy. Anal. Calcd (%) for C38H34Dy2N8O20S4 (1375.98): C 33.16; H 2.49; N 8.14%. Found: C 33.15; H 2.49; N 8.12%. IR (KBr, cm−1): 3438(w), 1663(s), 1453(w), 1384(m), 1235(w), 1177(w), 1131(m), 1055(s), 870(w), 691(m), 618(w). Preparation of [Ho2(Hsfpip)2(OH)2(H2O)6]n·2n(H2O) (6). Compound 6 was synthesized by a method similar to that of 5, except that Dy(NO3)3·6H2O was replaced by Ho(NO3)3·6H2O accordingly. Light yellow strip-like crystals of 6 were obtained, yield: 11.2 mg, 32.5% based on Ho. Anal. Calcd (%) for C38H30Ho2N8O20S4 (1376.80): C 33.05; H 2.48; N 8.11%. Found: C 33.06; H 2.49; N 8.12%. IR (KBr, cm−1): 3575(w), 3462(w), 1642(w), 1536(m), 1452(m), 1397(w), 1368(s), 1252(m), 1228(s), 1196(s), 1128(w), 1084(m), 1050(s), 1022(s), 832(w), 808(s), 737(m), 693(m), 619 (s), 518(m).

Scheme 1. Schematic Drawing for the Ligand H3sfpip

MOFs with outstanding structures. Notably, it contains a rigid phen plane and a flexible disulfonatophenyl group that could serve as a chelating and bridging ligand. Meanwhile, sulfonic group is easy to dissociate at very low pKa, which causes flexible coordination modes of SO3− ranging from μ1 to μ6.22 Furthermore, H3sfpip ligand has a large π-conjugated structure that helps to transfer energy as a nice chromophore. Based on the above considerations, H3sfpip can act as a good candidate for the construction of novel lanthanide-based coordination polymers. In this paper, we have synthesized ten new lanthanide coordination polymers based on H3sfpip, namely, [Pr(Hsfpip)(fum)0.5(H2O)]n·n(H2O)] (1), [Ln(Hsfpip)(glu)(H2O)2]n· n(H2O) (Ln = La (2), Pr (3), Sm (4)), [Ln2(Hsfpip)2(H2O)6]n·2n(H2O) (Ln = Dy (5), Ho (6), Er (7)), [La(Hsfpip)(adip) 0.5 (H 2 O) 2 ] n (8), [Y(Hsfpip)(suc)0.5(H2O)3]n·n(H2O) (9), and [Y(Hsfpip)(adip)0.5(H2O)2]n·n(H2O) (10). Furthermore, the luminescent and thermal stabilities of 1−10 have also been studied.

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EXPERIMENTAL SECTION

All commercially available chemicals and solvents are of reagent grade and were used as received without further purification. Ligand H3sfpip was synthesized according to literature methods.23 Infrared spectra were obtained from KBr pellets on a Bruker EQUINOX 55 Fourier transform infrared spectrometer in the 400−4000 cm−1 region. Elemental analyses (C, H, N) were performed on an elementar Vario EL III elemental analyzer. The 1H NMR and 13C NMR spectra were recorded on a Bruker Advance 300 or a Bruker DRX500 spectrometer in DMSO solution with TMS as internal standard. The solid-state photoluminescence analyses were performed on an Edinburgh FLS920 fluorescence spectrometer in the range of 200− 1400 nm. Thermal gravimetry analyses (TGA) were carried out with a Universal V2.6 DTA system at a rate of 10 °C/min in a nitrogen atmosphere. Powder X-ray diffraction (PXRD) measurements were measured on a Bruker D8 ADVANCE X-ray powder diffractometer (Cu Kα, 1.5418 Å). Synthesis of 2-(2,4-Disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline (H3sfpip). A mixture of benzaldehyde-2,4-disulfonic acid disodium salt (0.465 g, 1.5 mmol) 1,10-phenanthroline-5,6-dione (0.315 g, 1.5 mmol), ammonium acetate (2.31 g, 30 mmol), and glacial acetic acid (30 mL) was refluxed for 2 h, then cooled to room temperature, and diluted with water (ca. 60 mL). Dropwise addition of concentrated aqueous ammonia gave a yellow precipitate, which was collected and washed with water followed by vacuum drying to give the ligand in 56.49% yield (0.274 g). Anal. Calcd (%) for C19H12N4O6S2 (700.37): C 49.9; H 2.65; N 12.27%. Found: C 50.00; H 2.69; N 12.29%. IR (KBr, cm−1): 3525(m), 3433(w), 3221(m), 1646(w), 1569(m), 1509(m), 1448(s), 1399(s), 1297(w), B

DOI: 10.1021/acs.cgd.5b00117 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Table 1. Crystal Data and Structural Refinement Parameters for 1−10 empirical formula formula wt cryst syst space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z ρcalc (g·cm−3) μ (mm−1) F (000) reflns collected reflns unique R(int) params S on F2 R1, wR2 [I > 2σ(I)] R1, wR2 (all data) Δρmax, Δρmin (e·Å−3) empirical formula formula wt cryst syst space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z ρcalcd (g·cm−3) μ (mm−1) F (000) reflns collected reflns unique R(int) parameters S on F2 R1, wR2 [I > 2σ(I)] R1, wR2 (all data) Δρmax, Δρmin (e·Å−3)

1

2

3

4

5

C21H11N4O11PrS2 700.37 monoclinic P21/c 12.8827(9) 8.2194(6) 23.9494(16) 90 103.971(1) 90 2460.9(3) 4 1.890 2.218 1376 12025 4351 0.0348 352 1.026 0.0304, 0.0692 0.0370, 0.0725 0.788, −0.458 6

C21.50H19LaN4O11S2 712.44 monoclinic C2/c 22.197(2) 16.1128(14) 15.4592(14) 90 119.595(1) 90 4818.8(7) 8 1.964 2.019 2824 11910 4272 0.0320 376 1.064 0.0282, 0.0658 0.0354, 0.0694 0.404, −0.398 7

C21.50H19N4O11PrS2 714.44 monoclinic C2/c 22.1467(18) 16.1377(13) 15.4746(13) 90 119.760(1) 90 4801.2(7) 8 1.977 2.276 2840 11647 4238 0.0291 375 1.036 0.0273, 0.0641 0.0333, 0.0674 0.446, −0.298 8

C21.50H17N4O11S2Sm 721.86 monoclinic C2/c 22.0274(16) 16.0790(16) 15.3889(12) 90 119.859(1) 90 4726.9(7) 4 2.029 2.735 2848 11533 4172 0.0274 369 1.027 0.0212, 0.0518 0.0234, 0.0531 0.446, −0.585 9

C38H34Dy2N8O20S4 1375.98 monoclinic P21/c 10.4285(9) 6.9527(5) 30.258(2) 90 96.4620(10) 90 2180.1(3) 4 2.096 3.687 1348 10258 3840 0.0306 346 1.030 0.0252, 0.0502 0.0301, 0.0523 0.519, −0.419 10

C21H20N4O12S2Y 673.44 triclinic P1̅ 8.1559(11) 11.6473(11) 14.3976(16) 110.607(2) 101.531(2) 93.7250(10) 1240.6(2) 2 1.803 2.593 682 6276 4341 0.0412 385 1.015 0.0525, 0.1067 0.0808, 0.1220 0.687, −0.470

C22H14N4O11S2Y 663.40 monoclinic P21/n 9.6057(12) 22.766(3) 11.7677(15) 90 107.889(2) 90 2449.0(5) 4 1.799 2.623 1332 12077 4323 0.0299 362 1.049 0.0442, 0.1162 0.0546, 0.1242 1.865, −1.112

C38H30Ho2N8O20S4 1376.80 monoclinic P21/c 10.490(2) 7.0119(15) 30.571(6) 90 96.552(3) 90 2234.0(8) 2 2.047 3.795 1344 10460 3939 0.0591 341 1.099 0.0389, 0.0931 0.0431, 0.0957 2.179, −1.351

C38H34Er2N8O20S4 1385.49 monoclinic P21/c 10.4411(8) 6.9518(6) 30.305(2) 90 96.552(1) 90 2185.5(3) 1 2.105 4.099 1356 10479 3861 0.0415 347 1.016 0.0292, 0.0613 0.0354, 0.0638 0.725, −0.551

C22H13LaN4O11S2 712.39 monoclinic P21/n 9.7714(8) 22.9583(17) 11.5707(9) 90 106.3600(10) 90 2490.6(3) 4 1.900 1.953 1400 13445 5081 0.0288 368 1.021 0.0346, 0.1206 0.0385, 0.1257 2.769, −0.890

container, which was heated to 180 °C for 3 days, and then slowly cooled to room temperature at a rate of 5 °C/h. The pale yellow sheet crystals of 8 were obtained, yield: 13.8 mg, 38.8% based on La. Anal. Calcd (%) for C22H13LaN4O11S2 (712.39): C 37.09; H 1.84; N 7.86%. Found: C 37.11; H 1.82; N 7.83%. IR (KBr, cm−1): 3441(w), 1636(w), 1567(m), 1446(s), 1402(s), 1229(s), 1174(s), 1125(w), 1083(s), 1031(s), 813(m), 736(m), 891(m), 670(s), 636(s), 548(w). Preparation of [Y(Hsfpip)(suc)0.5(H2O)3]n·n(H2O) (9). A mixture of Y(NO3)3·6H2O (19.1 mg, 0.05 mmol), H3sfpip (22.8 mg, 0.05 mmol), and H2suc (11.8 g, 0.1 mmol) in distilled water (12 mL) was stirred for 30 min in air, then sealed in a 25 mL Teflon-lined stainless steel container, which was heated to 180 °C for 3 days, and then slowly cooled to room temperature at a rate of 5 °C/h. The pale

Preparation of [Er2(Hsfpip)2(OH)2(H2O)6]n·2n(H2O) (7). Compound 7 was synthesized by a method similar to that of 5, except that Dy(NO3)3·6H2O was replaced by Er(NO3)3·6H2O accordingly. Pink block crystals of 7 were obtained, yield: 15.9 mg, 45.8% based on Er. Anal. Calcd (%) for C38H34Er2N8O20S4 (1385.49): C 32.94; H 2.47; N 8.08%. Found: C 32.95; H 2.49; N 8.02%. IR (KBr, cm−1): 3577(w), 3381(w), 1642(w), 1536(w), 1452(m), 1398(m), 1368(s), 1252(m), 1197(s), 1128(m), 1084(m), 1050(s), 1022(s), 831(m), 809(s), 737(m), 693(m), 619(m), 518 (m). Preparation of [La(Hsfpip)(adip)0.5(H2O)2]n (8). A mixture of La(NO3)3·6H2O (21.6 mg, 0.05 mmol), H3sfpip (22.8 g, 0.05 mmol), and H2adip (14.6 mg, 0.1 mmol) in distilled water (12 mL) was stirred for 30 min in air, then sealed in a 25 mL Teflon-lined stainless steel C

DOI: 10.1021/acs.cgd.5b00117 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 1. (a) The coordination environment of PrIII in 1. Lattice water and hydrogen atoms have been omitted for clarity (symmetry codes: A = −1 + x, 1 + y, z; B = −1 + x, y, z; C = 1 − x, 2 − y, −z; D = −x, 2 − y, −z). (b) The distorted tricapped trigonal prism coordination geometry of PrIII. (c) View of the 1D loop chain of 1. (d) View of the 2D layer structure of 1. (e) Schematic view of the 2D topology network: the dimetallic Pr(III) unit and Hsfpip2− anion are marked as blue and red, respectively. The fum2− anion is assigned to a linker and marked as green. yellow sheet crystals of 9 were obtained, yield: 16.2 mg, 48.1% based on Y. Anal. Calcd (%) for C21H20N4O12S2Y (673.44): C 37.45; H 2.99; N 8.31%. Found: C 37.42; H 3.01; N 8.28%. IR (KBr, cm−1): 3440(m), 1629(m), 1577(s), 1406(w), 1181(m), 1084(w), 1039(s), 737(m), 697(s), 640(m). Preparation of [Y(Hsfpip)(adip)0.5(H2O)2]n·n(H2O) (10). Compound 10 was synthesized by a method similar to that of 9, except that H2suc was replaced by H2adip. Yellow strip-like crystals of 10 were obtained, yield: 13 mg, 39.1% based on Y. Anal. Calcd (%) for C22H14N4O11S2Y (663.40): C 39.83; H 2.12; N 8.44%. Found: C 39.43; H 2.09; N 8.41%. IR (KBr, cm−1): 3432(m), 1584(s), 1468(m), 1452(s), 1420(s), 1365(m), 1316(m), 1229(s), 1179(s), 1127(s) 1085(s), 1038(s), 914(w), 816(m), 736(m), 694(m), 637(s), 548(m), 518(m), 492(s), 418(w). X-ray Crystallography. Intensity data were collected on a Bruker Smart APEX II CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Empirical absorption corrections were applied using the SADABS program. The structures were solved by direct methods and refined by full-matrix least-squares based on F2 using the SHELXTL-97 program package.24 All non-hydrogen atoms were refined anisotropically, and hydrogen atoms of organic ligands were generated geometrically. Crystal data and structural refinement parameters for 1−10 are summarized in Table 1, and selected bond distances and bond angles are listed in Table S1 (Supporting Information). Crystallographic data have been

deposited with the Cambridge Crystallographic Data Centre, CCDC Nos. 1045248−1045257. These data can be obtained free of charge via www.ccdc.can.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Centre, 12 Union Road, Cambridge CB2 1EZ, U.K., fax (+44) 1223-336033, or [email protected]).

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RESULTS AND DISCUSSION Description of Crystal Structures. Crystal Structure of [Pr(Hsfpip)(fum)0.5(H2O)]n·n(H2O) (1). The crystal structure analysis reveals that compound 1 crystallizes in the monoclinic system with P21/c space group and is a 2D layer structure. The asymmetric unit of 1 contains one crystallographically independent PrIII ion, one Hsfpip2− ligand, a half fum2− anion, one coordinated water molecule, and one lattice water molecule. As shown in Figures 1a and 1b, Pr1 is a nonacoordinated distorted tricapped trigonal prism coordination geometry formed by two nitrogen atoms (N1, N2) from one chelating Hsfpip2− ligand, two 2-SO3− oxygen atoms (O4A, O5D) and one 4-SO3− oxygen atom (O3C) from three different Hsfpip2− ligands, and four oxygen atoms (O7, O8, O8B, and O9) from two fum2− anions and one coordinated water molecule. The Pr−O and Pr−N bond lengths vary from 2.412(3) to 2.617(3) Å and 2.626(3) to 2.676(3) Å, D

DOI: 10.1021/acs.cgd.5b00117 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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crystallizes in the monoclinic system with C2/c space group and exhibits a 2D layer structure. The asymmetric unit of 3 contains one crystallographically independent PrIII ion, one Hsfpip2− ligand, a half glu2− anion, two coordinated water molecules, and one lattice water molecule. Pr1 is nonacoordinated by two nitrogen atoms (N1, N2) from one chelating Hsfpip2− ligand, two 4-SO3− oxygen atoms (O1A, O2A) and one 2-SO3− oxygen atom (O4B) from three different Hsfpip2− ligands, and four oxygen atoms (O7, O8, O9, and O10) from two glu2− anions and two coordinated water molecules, forming a distorted square antiprism coordination geometry, as shown in Figures 2a and 2b. The Pr−O and Pr−N bond lengths vary from 2.431(3) to 2.654(2) Å and 2.631(3) to 2.694(3) Å, respectively, and the angles of O−Pr−O and O− Pr−N range from 51.449(11)° to 151.35(8)° and 119.53(9)° to 144.62(10)°, respectively, which are closely similar to the values of compound 1. Comparing the average bond lengths and distances (Table S1 in the Supporting Information) of the Ln−O, Ln−N, and Ln−Ln for compounds 2−4, the corresponding distances decrease as the ionic radius of the Ln(III) ions decreases in the order La(III) > Pr(III) > Sm(III), which is consistent with the lanthanide contraction effect. Here, the Hsfpip2− ligand adopts a μ3-η2:η2:η1 coordination mode and the glu2− anion employs a bibidentate chelating coordination mode (Scheme 3, modes II and VII). Similarly to 1, two Hsfpip2− ligands in such a coordination mode join two Pr1 ions to form a {Pr2O2N4S2C16} 26-membered ring containing a type of pore with a size of ca. 15.630 Å × 12.747 Å based on the distances of Pr1···Pr1 and S1···S1, in which 4-SO3− groups participate. Then the rings are linked to its adjacent ones by means of 2-SO 3 − groups to form another kind of {Pr2O2N4S2C12} 22-membered ring containing a type of pore with a size of ca. 10.221 Å × 12.074 Å based on the distances of Pr1···Pr1 and C19···C19. Afterward, these two kinds of rings arranged alternately via Pr−O bonds to generate a 1D loop chain, as shown in Figure 2c. The adjacent 1D loop chains are further connected together by chelating glu2− anions to result in a 2D layer, as shown in Figure 2d. To further understand the structure of 3, Hsfpip2− ligand and Pr1 ion can be regarded as 3- and 4-connected nodes, respectively. The (glu)2− anion is assigned to a linker. Hence, compound 3 possesses a 2-nodal (3,4,)-connected 3,4L83 network with the point symbol of (42· 63·8)(42·6) (Figure 2e). Crystal Structure of [Ln2(Hsfpip)2(OH)2(H2O)6]n·2n(H2O) (Ln = Dy (5), Ho (6), Er (7)). The X-ray diffraction analyses reveal that compounds 5−7 are also isostructural. Here, the structure of 7 is described in detail to represent their frameworks. Compound 7 crystallizes in the monoclinic system with P21/c space group and possesses a 2D layer structure built up by dinuclear Er(III) units. The asymmetric unit of 7 contains one crystallographically independent ErIII ion, one Hsfpip2− ligand, one OH− anion, three coordinated water molecules, and one lattice water molecule. As shown in Figures 3a and 3b, Er1 is octacoordinated and surrounded by two nitrogen atoms (N1, N2) from one chelating Hsfpip2− ligand, two 4-SO3− oxygen atoms (O4B, O5A), two hydroxyl oxygen atoms (O7 and O7C), and two coordination water oxygen atoms (O8, O9). The coordination geometry can be described as a distorted bicapped trigonal prism. The Er−O and Er−N bond lengths vary from 2.214(3) to 2.440(3) Å and 2.499(4) to 2.526(4) Å, respectively, and the angles of O−Er−O and the O−Er−N range from 68.16(12)° to 141.61(11)° and 71.22(10)° to 148.62 (11)°, respectively, all of which are

respectively, and the angles of O−Pr−O and O−Pr−N range from 49.20(9)° to 141.69(9)° and 65.73(11)° to 154.22(10)°, which all correspond to those reported for other Pr(III) compounds.25 Here, the Hsfpip2− ligand adopts a μ4-η2:η1:η1:η1 coordination mode and the fum2− anion adopts a μ4-η2:η1:η2:η1 bridging coordination mode (Scheme 3, modes I and V). On Scheme 2. Reaction Routes of Compounds 1−10

Scheme 3. Coordination Modes of Hsfpip2− and Auxiliary Ligands in 1−10

the basis of these connection modes, two Pr(III) ions are linked by four sulfonyl groups from two Hsfpip2− ligands to form a binuclear {Pr2 O4 S 4C 6 } 16-membered ring with Pr···Pr separation of 9.708 Å. At the same time, a different type of {Pr2O2S2N4C12} 22-membered ring is also generated containing a type of pore with size of ca. 9.708 Å × 12.947 Å based on the distances of Pr1···Pr1 and C21···C21. These two kinds of rings are then linked through Pr1−O5 bonds and alternately arranged, leading to a 1D loop chain running along the a axis (Figure 1c). The adjacent 1D loop chains are then further connected by fum2− anions to give rise to a 2D layer framework (Figure 1d). To further understand the structure of 1, the topological analysis was carried out. For the sake of simplifying the whole structure at an optimum level, we select the dimetallic unit as a node rather than the single Pr(III) ion. Accordingly, the fum2− anion is a 2-connector which can be regarded as a linear linker and each Hsfpip2− ligand is a 3connecter because it links three dimetallic units. Each dimetallic unit is attached to another two dimetallic units through the fum2− anion bridges and six Hsfpip2− ligands, and thus can be treated as an 8-connected node. On the basis of the simplification principle,26 compound 1 possesses a 2-nodal (3,8)-connected 3,8L18 net with the point symbol of (3· 42)2(34·46·56·68·73·8) (Figure 1e). Crystal Structure of [Ln(Hsfpip)(glu)0.5(H2O)2]n·n(H2O) (Ln = La (2), Pr (3), Sm(4)). The X-ray diffraction analysis shows that compounds 2−4 are isostructural. Here, 3 is taken as an example to depict the structure in detail. Compound 3 E

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Figure 2. (a) The coordination environment of PrIII in 3. Lattice water and hydrogen atoms have been omitted for clarity (symmetry codes: A = −x, y, 0.5 − z; B = 0.5 − x, 0.5 − y, 1 − z). (b) The distorted square antiprism coordination geometry of PrIII. (c) View of the 1D loop chain of 3. (d) View of the 2D layer structure of 3. (e) Schematic view of the 2D 3,4L83 net: the Hsfpip2− anion and Pr1 ion are marked as aubergine and yellow, respectively.

Figure 3. (a) The coordination environment of ErIII ions in 7. Lattice water and hydrogen atoms have been omitted for clarity (symmetry codes: A = −x, 0.5 + y, 0.5 − z; B = −x, −0.5 + y, 0.5 − z; C = 1 − x, 2 − y, 1 − z). (b) The distorted bicapped trigonal prism coordination geometry of 7. (c) The linear [Er2(Hsfpip)2(OH)2] SBU. (d) View of the 2D layer structure of 7. (e) Schematic view of the 2D kgd net: the Hsfpip2− anions and dimetallic units are marked as green and purple, respectively.

comparable to other reported Er(III) compounds.27 Comparing the average distances (Table S2 in the Supporting

Information) of the Ln−O, Ln−N, and Ln−Ln for the compounds 5−7, the corresponding distances decrease as the F

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Figure 4. (a) The coordination environment of LaIII in 8. Hydrogen atoms have been omitted for clarity (symmetry codes: A = 0.5 − x, −0.5 + y, 1.5 − z; B = −1.5 + x, 1.5 − y, −0.5 + z; C = −1 − x, 1 − y, 1 − z). (b) The distorted bicapped square antiprism coordination sphere of 8. (c) The bimetallic unit in 8. (d) Representation of the formation of pillared-layer structures and the pcu topology network for 8.

anion, a half adip2− anion, and two coordinated water molecules. La1 shows a distorted bicapped square antiprism coordination geometry composed of two nitrogen atoms (N1, N2) from one chelating Hsfpip2− ligand, two 4-SO3− oxygen atoms (O1A, O2B) from two different Hsfpip2− ligands, three oxygen atoms from two different adip2− anions (O7C, O8C, and O7), and two coordinated water oxygen atoms (O9, O10), as shown in Figures 4a and 4b. The La−O and La−N bond lengths vary from 2.454(3) to 2.733(3) Å and 2.710(3) to 2.787(3) Å, respectively, and the angles of O−La−O and O− La−N range from 69.43(11)° to 146.41(10)° and 71.23(10)° to 143.30(10)°, respectively, which are similar to that of compound 2. In 8, the Hsfpip2− ligand adopts a μ3-η2:η1:η1 bridging coordination mode III (Scheme 3) and the auxiliary adip2− ligand employs a μ4-η1:η2:η1:η2 coordination fashion IX (Scheme 3). Two neighboring LaIII ions are quadruply bridged by carboxylate and sulfonic groups from two adip2− and two Hsfpip2− anions respectively to yield a binuclear La(III) unit with the La···La distance of 4.357 Å (Figure 4c). The bimetallic units are cross-linked to each other by antiparallel Hsfpip2− anions to form a 2D grid-shaped framework (Figure 4d), and each grid is a rhombus with a size of 26.576 Å × 20.753 Å.

ionic radius of the Ln(III) ions decreases in the order Dy(III) > Ho(III) > Er(III), which is consistent with the lanthanide contraction effect. It is worth noting that two Er1 ions are connected by two oxgen atoms (O7) which come from the hydroxyl groups to form a rhombic dierbium unit, in which the Er1···Er1 separation is 3.674 Å. Such units are then fitted together by phenanthroline groups to make up the linear [Er2(Hsfpip)2(OH)2] SBU (Figure 3c). Each Hsfpip2− anion adopts μ3-η2:η1:η1 coordination mode III (Scheme 3) and extends these staggered SBUs into a 2D layer structure through Er1−O4B and Er1−O5A bonds (Figure 3d). Topologically, the Hsfpip2− anion and dimetallic unit can be regarded as 3- and 6connected nodes, respectively, and compound 7 possesses a 2nodal (3,6)-connected kgd net with the point symbol of (43)2(46·66·83) which is calculated by TOPOS (Figure 3e). Crystal Structure of [La(Hsfpip)(adip)0.5(H2O)2]n (8). Singlecrystal X-ray diffraction study reveals that compound 8 greatly differs from 1−7 and possesses an appealing 3D pillared-layer structure containing La-phenanthroline layers and dicarboxylate pillars, which crystallizes in the monoclinic system with space group P21/n. The asymmetric unit of 8 contains one crystallographically independent La(III) ion, one Hsfpip2− G

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Figure 5. (a) The coordination environment of YIII in 9. Lattice water and hydrogen atoms have been omitted for clarity (symmetry codes: A = x, 1 + y, 1 + z; B = 1 − x, 2 − y, 2 − z). (b) The distorted bicapped trigonal prism coordination sphere of 9. (c) The 2D layer connected by suc2− anions. (d) The view of the 2D bilayer structure. (e) The view of the 3D framework of 9. (f) Schematic view of the 2D sql net: the dimetallic units are marked as green.

Figure 6. (a) The coordination environment of YIII in 10. Lattice water and hydrogen atoms have been omitted for clarity (symmetry codes: A = −1.5 + x, 0.5 − y, −0.5 + z; B = 2.5 − x, 0.5 + y, 0.5 − z; C = 1 − x, 1 − y, −z). (b) The distorted bicapped trigonal prism coordination sphere of 10. (c) Representation of the formation of pillared-layer structures and the pcu topology network for 10. H

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Figure 7. Solid state emission spectra of 1−10 (a−j) at room temperature.

Further, these 2D layers are pillared by adip2− anions to give rise to an infinite 3D network structure. Topologically, the framework of 8 presents a 6-connected pcu network with the point symbol of (412·63), when considering the La2 dimer as a 6-connected node (Figure 4e). Crystal Structure of [Y(Hsfpip)(suc)0.5(H2O)3]n·n(H2O) (9). X-ray crystallographic analysis reveals that compound 9 crystallizes in the triclinic system with P1̅ space group and is a 2D bilayer structure. The asymmetric unit of 9 contains one crystallographically independent Y(III) ion, one Hsfpip2− ligand, a half suc2− anion, three coordinated water molecules, and one lattice water molecule. Y1 is an octacoordinated

distorted bicapped trigonal prism coordination sphere formed by two nitrogen atoms (N1, N2) from one chelating Hsfpip2− ligand, one 4-SO3− oxygen atom (O5D), one oxygen atom (O7) from suc2− anion, and four coordination water oxygen atoms (O8B, O9, O10, and O11), as shown in Figures 5a and 5b. The Y−N bond lengths vary from 2.524(4) to 2.554(4) Å, and the Y−O bond lengths range gradually from 2.296(4) to 2.372(4) Å, respectively. The angles of O−Y−O and the O− Y−N range from 72.17(14)° to 148.12(13)° and 72.55(14)° to 146.49(15)°, respectively, which all correspond to those reported for other Y(III) compounds.28 Each Hsfpip2− ligand adopting the μ2-η2:η1 bridging coordination mode IV (Scheme I

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ligand does not appear in the final structure of 5−7. In order to explore the effect of auxiliary ligand, we carried out the same reactions in the absence of auxiliary ligand. However, the products are faint yellow precipitates rather than crystals. Therefore, we propose that the secondary ligands may play a significant role as a template in the formation of 5−7. In order to make further comparison of the influence of the coordination flexibility on the structures, H2suc and H2adip were added in the synthetic processes of 9 and 10, respectively. Different structures of 2D layer and 3D network were obtained. Based on the aforementioned facts, it is found that the auxiliary ligand has significant effects on the formation and structures of the resulting compounds. As mentioned concisely in the Introduction, Zhao et al. reported six 0D or 1D transition metal−organic supramolecular compounds constructed from the common 1H-imidazo(4,5f)(1,10)-phenanthroline ligand, showing excellent luminescent properties.9 Subsequently, Zhang et al. reported three isostructural 1D lanthanide-organic frameworks with 2,2′diphenyldicarboxylate as the bridging ligand and 1H-imidazo(4,5-f)(1,10)-phenanthroline as the auxiliary chelating ligand.10 In addition, Liu et al. reported a 1D copper(II) coordination polymer generated from 4,4′-diphenyldicarboxylate and 2-(2carboxyphenyl)imidazo(4,5-f)(1,10)-phenanthroline ligands, displaying good photocatalytic property for organic dyes.15 Compared with these splendid achievements, it is the first time that a series of lanthanide coordination polymers with versatile 2D or 3D structures based on the disulfonatophenyl group derivative of 1,10-phen and different auxiliary ligands is reported. Luminescent Properties. The lanthanide coordination polymers may possess excellent luminescent properties in terms of their line-like and high color-pure emissions. Hence, the solid-state luminescent properties of compounds 1−10 are investigated at room temperature (see Figure 7). Meanwhile, the excitation spectra for 1−10 are given in Figure S2 in the Supporting Information. As shown in Figures 7a and 7c, compounds 1 and 3 exhibit characteristic emission bands of Pr(III) ions in the visible region. Upon excitation at 320 nm, we observed four emission bands at nearly 435, 483, 506, and 598 nm, which are attributed to 3P0 → 3H4, 3P0 → 3H5, 3P0 → 3H6, and 1D2 → 3H4 transitions, respectively. When excited at 380 nm, compound 4 displays three characteristic bands of 4G5/2 → 6 H5/2 (563 nm), 4G5/2 → 6H7/2 (600 nm), and 4G5/2 → 6H9/2 (644 nm) of the Sm(III) ion. Meanwhile, the ligand-centered transition (π* → π) is stronger at 511 nm, indicating the ineffective sensitization from the H3sfpip ligand to the Sm3+ centers. The enhancement and blue shift of this emission band (Figure 7d) compared to that of the free ligand (521 nm) may result from the coordination of the ligand to the metal ions.29 With regard to compound 5, the emission spectra excited at 395 nm presents three typical emission bands of Dy(III) ions, which are attributed to 4F9/2 → 6H15/2 (481 nm), 4F9/2→6H13/2 (572 nm), and 4F9/2→6H11/2 (615 nm) transitions. It is noteworthy that the ligand-centered emission is totally quenched, indicating that the triplet state of (Hsfpip)2− matches well with the excited state of DyIII ion and the energy transfer from the ligand to DyIII ion is efficient. Upon excitation at 290 nm, a relatively broad emission band is observed at 504 nm for compound 6, which is attributed to intraligand charge transfer. When excited at 315 nm, the emission spectrum of compound 7 exhibits in the 450−550 nm region with the maximum wavelength of 498 nm, which corresponds to the

3) connects to two Y1 ions to form a 1D zigzag chain through the phenanthroline group and the 4-SO3− oxygen atom (Figure S1 in the Supporting Information). Then, adjacent 1D chains are linked by suc2− anions to give rise to a 2D layer (Figure 5c). Interestingly, these 2D layers are parallel to each other and arranged in a staggered pattern running along the b axis to generate a 2D bilayer structure (Figure 5d). Finally, the neighboring 2D bilayers connect with each other through intermolecular hydrogen bonding interaction (O4···H4−O10 = 2.356 Å) and further stacked in an AAA fashion resulting in a 3D supramolecular architecture (Figure 5e). The topological analysis was carried out to get insight into the structure of 9. If we consider the bi-Y unit as a 4-connected node, while both the Hsfpip2− and suc2− anions serve as linkers, the overall structure of 9 is a 4-connected sql net with the point symbol of (44·62) (Figure 5f). Crystal Structure of [Y(Hsfpip)(adip)0.5(H2O)2]n·n(H2O) (10). When H2adip was used as the auxiliary ligand instead of H2suc, compound 10 was obtained. X-ray crystallographic analysis reveals that compound 10 crystallizes in the monoclinic system with P21/n space group and exhibits an intriguing 3D pillaredlayer structure. The asymmetric unit of 10 contains one crystallographically independent Y(III) ion, one Hsfpip2− ligand, a half adip2− anion, two coordinated water molecules, and one lattice water molecule. As shown in Figures 6a and 6b, Y1 is octacoordinated to two nitrogen atoms (N1, N2) from one chelating Hsfpip2− ligand, two 4-SO3− oxygen atoms (O4B, O6C), one oxygen atom (O7) from one adip2− anion, and three coordination water oxygen atoms (O8, O9, and O10), resulting in a distorted bicapped trigonal prism coordination sphere similar to 9. The Y−O and Y−N bond lengths vary from 2.191(4) to 2.461(3) Å and 2.531(4) to 2.616(4) Å, respectively. The angles of O−Y−O and the O−Y−N range from 72.17(14)° to 148.12(13)° and 70.76(11)° to 146.93(14)°, respectively, which are all similar to compound 9. Here, the Hsfpip2− ligand adopts a μ3-η2:η1:η1 coordination mode and the adip2− anion adopts a μ4-η1:η1:η1:η1 bridging coordination mode (Scheme 3, modes III and VIII), which take on some similarities to that of 5−8. On the basis of this coordination fashion, the Hsfpip2− ligands and adip2− anions link Y(III) ions into a 2D grid-shaped layer, and then the resulting layers are further pillared by the adip2− anion to give rise to an infinite 3D “pillared-layer” structure (Figure 6d). Considering the Y2 dimers as nodes, the whole structure can be simplified to a 6-connected pcu topology with the point symbol of (412·63). Analysis and Comparison of Synthetic Conditions and Structures. All the compounds were prepared under hydrothermal conditions and obtained in moderate yield. The reaction route of 1−10 is shown as Scheme 2. Compounds 2− 4 are isostructural. Compared with 1, the auxiliary H2glu acid was used, instead of H2fum acid, and the different 2D layer structure based on alternately arranged loop chains was obtained. In addition, we did a series of experiments by changing the auxiliary ligand to oxalic acid, adipic acid, and other aromatic acids, which only lead to precipitates rather than crystals. The result demonstrates that length and configuration, as well as the steric effect of auxiliary ligand, are important for crystal growth in the reaction system. Compounds 5−7 are also isostructural and show a 2D layer structure stemming from dinuclear metallic units with the hydroxyl groups as a bridge. We also added a series of aliphatic dicarboxylic acid as an auxiliary ligand in this system, but it is regrettable that auxiliary J

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and adip2− anions (obsd 28.52%, calcd 83.98%). For compound 9, it released lattice and coordinated water molecules before 190 °C and then began to decompose upon further heating. The weight loss of 77.09% is attributed to the decomposition of organic components (calcd 76.07%). The TGA curve of 10 is similar to that of 9 and shows a two-step weight loss. The first weight loss of 18.91% below 200 °C is consistent with the removal of lattice and coordinated water molecules and adip2− anions (calcd 19.00%). Then the framework is stable to nearly 500 °C, where a continuous weight loss of 77.98% was observed from 500 to 880 °C, which can be ascribed to the decomposition of Hsfpip2− ligands (calcd 79.67%). The residue product of 13.16% is yttrium oxide (calcd 13.40%). TGA results of 1−10 indicate that they all possess great thermal stability (Figure S6, Supporting Information, shows the TG curves for 1−10).

intraligand charge transfer. The blue shifts for both 6 and 7 may be caused by the existence of Ln−sfpip coordination bonds.30 Compounds 2, 8, 9, and 10 only exhibit ligand-centered emission bands. Upon excitation at 380 nm, intense emission is observed at 505 nm, 429 nm, 429 nm, and 423 nm for 2, 8, 9, and 10 respectively, which may be assigned to the intraligand transition of the ligand. The slightly enhancement of luminescence intensity compared to the free ligand is perhaps a result of the metal−ligand coordination which effectively increases the rigidity of the ligand and reduces the nonradiative decay of the intraligand excited state.31,32 Furthermore, the emission decay lifetimes of compounds 4 and 5 were measured and the curves (Figures S3 and S4 in the Supporting Information) are best fitted by biexponentials in the solid state. The emission decay lifetimes are τ1 = 2.76 μs (13.85%) and τ2 = 8.21 μs (86.15%) (χ2 = 1.152, Figure S2 in the Supporting Information) for 4, τ1 = 5.57 μs (15.25%) and τ2 = 9.96 μs (84.75%) (χ2 = 1.048, Figure S3 in the Supporting Information) for 5, respectively. The intensities of energy transitions from the ligand to lanthanide ions change in the order Dy(III) > Sm(III). It means that the energy transfer from (Hsfpip)2− anions to Dy(III) is more effective than that to Sm(III), which may be due to the different energy gaps of various lanthanide ions.33,34 PXRD and Thermogravimetric Analysis. The powder Xray diffraction of compounds 1−10 were checked for the crystalline samples at room temperature. As shown in Figure S5 in the Supporting Information, the peak positions of experimental and simulated PXRD patterns match well, which confirms their phase purity. To study the thermal stabilities of these compounds, thermal gravimetric analysis (TGA) of 1−10 was performed. TGA curves have been obtained under an N2 atmosphere for crystalline samples of the selected compounds in the temperature range 33−1000 °C with a heating rate of 10 °C/min. Compound 1 first lost its lattice and coordinated water molecules below 186 °C; the weight loss of 2.47% and 5.05% was consistent with that calculated (2.57% and 5.14%). The framework is stable up to 355 °C, after which temperature the framework begins to collapse, accompanied by the decomposition of the organic components and suc2− anions, at 355 °C and ending at 715 °C; the weight loss of 64.47% and 13.55% was consistent with that calculated (64.88% and 13.69%). Because of the similarity of the structures for 2−4 and 5−7, compounds 2 and 6 were selected as representatives for thermogravimetric analysis (TGA) to examine the thermal stabilities. The TG curve of 2 shows an initial weight loss of 7.42% before 200 °C, corresponding to the removal of lattice and coordinated water molecules (calcd 7.58%). Then the framework is stable to 450 °C, where a continuous weight loss of 64.92% was observed from 450 to 700 °C, which can be ascribed to the organic components (calcd 65.06%). Compound 6 shows a continuous weight loss of 10.30% in the temperature range 33−196 °C, which is attributed to the loss of a lattice water molecule, coordinated water molecule, and OH− anions (calcd 10.28%). The network of this compound started to decompose when the temperature was higher than 470 °C. The remaining weight corresponds to the formation of dysprosium oxide (obsd 28.52%, calcd 27.05%). The TGA curve of 8 shows an initial weight loss of 5.23% before 198 °C, corresponding to the removal of coordinated water molecules (calcd 5.05%). The framework is stable up to 330 °C and then begins to collapse, corresponding to the loss of Hsfpip2− ligands

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CONCLUSIONS In summary, ten new Ln(III)-based coordination polymers with H3sfpip and a series of aliphatic dicarboxylic acid have been successfully prepared under hydrothermal conditions. The compounds 1−10 present fascinating 2D and 3D structures. The results of the present work indicate that it is a feasible strategy to further design metal−organic compounds with new structures and properties through rational introduction of the second ligand. In particular, compounds 1 and 3 exhibit characteristic emission bands of Pr(III) ions in the visible region. Meanwhile, compounds 4 and 5 respectively display characteristic emission bands of Sm(III) and Dy(III) with lifetimes at the microsecond scale, indicating their potential application in the field of luminescence.

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ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic files in CIF format, selected bond distances and bond angles for 1−10, the view of 1D loop chain inside 9, the excitation spectra for compounds 1−10, the fitted decay curves of 4 and 5, PXRD patterns, and thermal analyses. This material 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]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant Nos. 21173164 and 21473133). REFERENCES

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Crystal Growth & Design

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DOI: 10.1021/acs.cgd.5b00117 Cryst. Growth Des. XXXX, XXX, XXX−XXX