Cd-MOFs Featuring Topological Variation

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Rational Assembly of Co/Cd-MOFs Featuring Topological Variation Hao Wang,†,§,‡ Fei-Yan Yi,†,§ Song Dang,† Wan-Guo Tian,†,‡ and Zhong-Ming Sun*,† †

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin 130022, China ‡ School of Chemistry & Environmental Engineering, Changchun University of Science & Technology, Changchun 130022, China S Supporting Information *

ABSTRACT: Three different carboxylate ligands of 4,4′-biphthalic acid (H4L, linear), 4,4′-axydiphthalic acid (H4LO, V-shaped), and thiophene-2,5-dicarboxylic acid (H2LS, V-shaped and heteroatomic ring) were selected as two-connected nodes to react with Co(II) or Cd(II) nitrates in the presence of 1,3,5-tris(1-imidazolyl)benzene (tib, Y-shaped and tridentate). Hydrothermal reactions in distilled water afforded seven new Co(Cd)-MOFs, namely, M(tib)(H2L)(H2O)2·H2O (M = Co, 1; Cd, 2), M2(tib)2(H2LO)2(H2O)2 (M = Co, 3; Cd, 4), Co2(tib)(LO)·H2O (5), Co(tib)(LS)·2H2O (6), and Cd(tib)(LS)·3H2O (7). Of particular interest, they exhibit four interesting nets. 1−2 and 3−4 feature binodal (3,4) and (3,3,4,4)connected nets if H-bonds are taken into account, respectively. 5 is composed of a two-dimensional metal-LO layer and a onedimensional metal-tib chain and simplified into a 4-nodal (3,4,4,5)-connected net. 6 and 7 feature rare binodal (3,5)-connected {3.72}{32.75.83} fsf/polar net and (3,5)-connected {63}{69.8} hms net. Structural analyses show that each type of compound with the same metal components and tib ligands exhibit such interesting topological variations, which are derived from different orientations of three carboxylate ligands. Other properties of these compounds were also investigated, such as elemental and thermogravimetric analyses, photoluminescent spectroscopy, and magnetic behavior.

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INTRODUCTION Over the past two decades, metal−organic frameworks (MOFs) known as a new class of well-ordered porous crystalline materials have attracted intense interest.1,2 The motivation not only comes from their tremendous potential applications,3−8 such as gas storage and separation,3 drug delivery,4 optical properties,5 and catalysis,6 etc., but also is owed to their intriguing variety of architectures and topologies.7 They are comprised of metal ions or cluster nodes connected by organic ligands. By judicious selection or design of metal center (or clusters) and organic linkers with fixed geometry, MOFs with predesigned structural topology can be rationally assembled. So the predesigned organic ligand is a vital component in an appropriate arrangement, whose encoded information is read by the metal ions according to their coordination tendency, although small changes, such as the effect of solvents and the coordination environment of metal ions, can be also attributed to the final structures. A careful examination of reported coordination polymers, reveals that binodal topological networks, such (3,4)-, (3,5)-, (3,6)-connected networks, are relatively rare compared to uninodal networks, especially for 5 and higher-connected networks.9 Bearing the aforementioned ideas in mind, we selected tib (C3 symmetry) as the main ligand, which is a rigid Y-shaped Ndonor ligand and able to bind metal ions forming layered structures. The layers can be further bridged by secondary carboxylic acid, forming three-dimensional (3D) topological © 2013 American Chemical Society

nets. Such dual-ligand strategy offers greater tunability for the construction of target frameworks than using a single ligand. Among various types of organic carboxylic acids, three ligands (H4L, H4LO, and H2LS, shown in Scheme 1) were selected with Scheme 1. Structures of Ligands tib, H4L, H4LO, and H2LS

different angles of two carboxylate groups. From a structural point of view, H4L is linear, H4LO is V-shaped and O-bridging, H2LS is V-shaped and a heteroatomic ring with a S atom. The reason is that the bigger radius and their lone pair of electrons for the O and S atoms of H4LO and H2LS ligands can be more easily delocalized,10 and V-shaped configuration are apt to Received: September 5, 2013 Revised: November 12, 2013 Published: December 3, 2013 147

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Table 1. Crystal Data for 1−7 compounds

1

2

3

4

chemical formula structural formula fw temperature (K) a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z space group crystal system 2θ max (deg) μ(Mo Kα) (mm−1) D (g/cm3) F(000) reflections collected R1a [I > 2σ(I)] wR2b [I > 2σ(I)] GOF

C31H26CoN6O11 Co(tib)(H2L)(H2O)2·H2O 717.51 273(2) 7.2162(3) 16.0626(6) 26.1991(10 90 91.9750(10) 90 3035.0(2) 4 P21/c monoclinic 52.22 0.640 1.570 1476 16592 0.0411 0.1143 1.045

C31H26CdN6O11 Cd(tib)(H2L)(H2O)2·H2O 770.98 273(2) 7.2450(4) 16.1456(8) 26.6414(13) 90.00 91.8990(10) 90.00 3114.7(3) 4 P21/c monoclinic 52.20 0.774 1.644 1560 16953 0.0414 0.1099 1.008

C62H44Co2N12O20 Co2(tib)2(H2LO)2(H2O)2 1394.95 273(2) 15.8744(12) 12.6089(9) 27.9469(19) 90 94.0760(10) 90 5579.7(7) 4 P21/n monoclinic 52.14 0.691 1.661 2856 30279 0.0516 0.1120 1.013 6

C62H44Cd2N12O20 Cd2(tib)2(H2LO)2(H2O)2 1501.89 273(2) 15.9719(13) 12.9270(10) 27.989(2) 90 94.8830(10) 90 5758.0(8) 4 P21/n monoclinic 52.30 0.833 1.733 3024 31393 0.0591 0.1340 1.059 7

5 chemical formula structural formula fw temperature (K) a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z space group crystal system Flack 2θ max (deg) μ(Mo−Kα) (mm−1) D (g/cm3) F(000) reflections collected R1a [I > 2σ(I)] wR2b [I > 2σ(I)] GOF a

C31H20Co2N6O10 Co2(tib)(LO)·H2O 754.39 106(2) 7.3615(5) 11.5150(8) 17.6730(12) 94.3420(10) 101.2670(10) 97.9440(10) 1446.97(17) 2 P1̅ triclinic

C21H18CoN6O6S Co(tib)(LS)·2H2O 541.40 273(2) 18.296(2) 9.8044(11) 13.0202(15) 90.00 90.00 90.00 2335.6(5) 4 Pca21 orthorhombic −0.038(19) 52.28 0.875 1.540 1108 12556 0.0422 0.0976 0.992

52.14 1.221 1.731 764 8034 0.0405 0.0985 1.032

C21H20CdN6O7S Cd(tib)(LS)·3H2O 612.89 293(2) 10.7320(11) 20.421(2) 22.125(2) 90 90 90 4849.0(8) 8 Pbca orthorhombic 52.14 1.041 1.679 2464 22514 0.0450 0.1107 1.023

R1 = ∑||Fo| − |Fc||/∑|Fo|. bwR2 = {∑w[(Fo)2 − (Fc)2]2/∑w[(Fo)2]2}1/2.

Their formulas were confirmed by elemental analyses, singlecrystal X-ray diffraction, and thermogravimetric analyses (TGA). Different carboxylate coligands were carefully and purposefully selected to adjust the final interesting topological nets. The details of their syntheses, structures, photoluminescent spectroscopy, and magnetic properties are reported below.

establish bridges to extend 3D directions. With polycarboxylic acid as the coligand pillared into the metal-tib layer, the metal centers will be constructed into 5 or higher-connected nodes. On the basis of this point, tib as a tritopic ligand links metal centers to give a basic 3-connected tib-M framework. Meanwhile, three different carboxylate groups (Scheme 1) were selected as linkers into tib-M species to construct porous frameworks and new types of topological networks. Hydrothermal reactions in distilled water afforded seven new MOFs, namely, M(tib)(H2L)(H2O)2·H2O (M = Co, 1; Cd, 2), M2(tib)2(H2LO)2(H2O)2 (M = Co, 3; Cd, 4), Co2(tib)(LO)· H2O (5), Co(tib)(LS)·2H2O (6), and Cd(tib)(LS)·3H2O (7).

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EXPERIMENTAL SECTION

Materials and General Methods. All chemicals and solvents during the synthesis processes of compounds 1−7 were purchased commercially and used without further purification. C, H, and N 148

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H2LS) for 6 and ∼61% (based on H2LS) for 7. Elemental analysis calcd (%) for C21H18CoN6O6S 6 (Mr = 541.40): C, 46.59; H, 3.35; N, 15.52. Found: C, 45.62; H, 3.40; N, 15.75. Elemental analysis calcd (%) for C21H20CdN6O7S 7 (Mr = 612.89): C, 41.15; H, 3.29; N, 13.71. Found: C, 41.47; H, 3.35; N, 13.33. Selected IR peaks (cm−1) for 6: 3138 (w), 1615 (w), 1575 (m), 1510 (s), 1334 (m), 1238 (m), 1072 (s), 1017 (s), 937 (m), 756 (m) (see Figure S2 of the Supporting Information). Selected IR peaks (cm−1) for 7: 3127 (w), 1614 (w), 1504 (s), 1358 (s), 1248 (m), 1117 (m), 1072 (m), 1007 (m), 936 (m), 815 (m), 755 (s) (see Figure S2 of the Supporting Information). X-ray Crystal Structure Determination. Single crystals of complexes 1−7 with appropriate dimensions were selected under an optical microscope and were mounted on a glass fiber for data collection. Crystallographic data were carried out on a Bruker Apex II CCD diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71073 Å). Data reduction were performed with SAINT. All absorption corrections were applied using the multiscan program SADABS.12 All structures were solved by direct methods using SHELXS-97 of the SHELXTL package and refined by the full-matrix least-squares method with SHELXTL-97.13 All of the nonhydrogen atoms in the seven structures were found from the difference Fourier map and refined with anisotropic displacement parameters. The hydrogen atoms associated with the organic molecules were placed in calculated positions and were added to the structure factor calculation. A summary of the pertinent crystallographic data collection and refinement paramenters for the seven complexes is listed in Table 1. Selected bond lengths are collated in Table 2. The CCDC reference numbers are 959077−959083 for 1−7. More details on the crystallographic studies are given in the Supporting Information. Topological analysis of all complexes were performed by TOPOS.14

analyses were performed with a Perkin−Elmer 2400 elemental analyzer. The IR (diamond) spectra were recorded on a Nicolet 7600 Fourier-transform infrared (FT-IR) spectrometer. Powder X-ray diffraction (PXRD) data were recorded on a D8 Focus (Bruker) diffractometer with Cu Kα radiation field-emission (λ = 0.15405 nm, continuous, 40 kV, 40 mA, increment = 0.02°). Thermogravimetric and differential thermal analysis (TG-DTA) data were carried out on a Thermal Analysis Instrument (SDT 2960, TA Instruments, New Castle, DE) from room temperature to 800 °C under air atomosphere at a heating rate of 10 °C/min. The fluorescent spectra were measured on a Hitachi F-4500 fluorescence spectrophotometer equipped with a 150 W xenon lamp as the excitation source. Temperature-dependent magnetic measurements were peformed on a Quantum Design SQUID MPMS-7 magnetometer with an applied field of 1000 Oe. The magnetic data were corrected for the susceptibility of the holder and the diamagnetic contributions of the sample using Pascal constants.11 Preparation of Complexes 1−7. Syntheses of M(tib)(H2L)(H2O)2·H2O (M = Co, 1; Cd, 2). A mixture of Co(NO3)2·6H2O (0.12 mmol, 34.9 mg), tib (0.08 mmol, 22.2 mg), H4L (0.08 mmol, 26.4 mg), and 6 mL distilled water (H2O) was sealed in a 20 mL pressureresistant Teflon-lined stainless steel vessel, heated in an oven to 130 °C for three days, and then slowly cooled to room temperature in 20 h. The red crystals of 1 and colorless crystals of 2 were obtained in the yields of 19.5 mg (68% based on H4L) and 15.4 mg (50% based on H4L), washed with water, and dried at room temperature. Their purities were confirmed by X-ray power diffraction (XRD) (see Figure S1 of the Supporting Information). Elemental analysis calcd (%) for C31H26CoN6O11 1 (Mr = 717.51): C, 51.89; H, 3.65; N, 11.71. Found: C, 51.67; H, 3.32; N, 11.79. Elemental analysis calcd (%) for C31H26CdN6O11 2 (Mr = 770.98): C, 48.29; H, 3.40; N, 10.90. Found: C, 48.01; H, 3.53; N, 11.12. Selected IR peaks (cm−1) for 1: 3142 (w), 1680 (w), 1509 (s), 1364 (s), 1258 (m), 1072 (m), 1012 (m), 932 (m), 867 (m), 826 (m), 796 (m), 771 (m) (see Figure S2 of the Supporting Information). Selected IR peaks (cm−1) for 2: 3116 (w), 1700 (w), 1619 (w), 1338 (s), 1248 (w), 1107 (w), 1072 (m), 926 (w), 846 (m), 790 (w), 755 (m), 705 (w) (see Figure S2 of the Supporting Information). Syntheses of the M2(tib)2(H2LO)2(H2O)2 (M = Co, 3; Cd, 4) and Co2(tib)(LO)·H2O (5). Compounds 3−4 could also be readily synthesized and a similar procedure was followed as described for 1−2, except that the carboxylate ligand was changed to H4LO with higher reaction temperature (160 °C); 3 and 4 were recovered in the form of red bulk crystals and colorless needle crystals, respectively, with the yield of ∼75% (based on Co) and ∼81% (based on Cd). The initial pH value of solution is adjusted to 6.7 by the addition of 1 M NaOH solution, and purple brick crystals of 5 could be isolated instead of 3 with a yield of 9.0 mg (30% based on Co). Their purities were also confirmed by X-ray power diffraction (XRD) (Figure S1 of the Supporting Information). Elemental analysis calcd (%) for C62H44Co2N12O20 3 (Mr = 1394.95): C, 53.38; H, 3.18; N, 12.05. Found: C, 53.47; H, 3.06; N, 12.00. Elemental analysis calcd (%) for C62H44Cd2N12O20 4 (Mr = 1501.89): C, 49.58; H, 2.95; N, 11.19. Found: C, 49.19; H, 3.01; N, 11.31. Elemental analysis calcd (%) for C31H20Co2N6O10 5 (Mr = 754.39): C, 49.36; H, 2.67; N, 11.14. Found: C, 49.55; H, 2.52; N, 11.31. Selected IR peaks (cm−1) for 3: 3112 (w), 1690 (s), 1619 (w), 1549 (w), 1504 (s), 1358 (m), 1262 (s), 1222 (m), 1077 (s), 1011 (w), 971 (w), 826 (s), 765 (s) (see Figure S2 of the Supporting Information). Selected IR peaks (cm−1) for 4: 3121 (w), 1685 (m), 1619 (w), 1504 (s), 1348 (m), 1262 (s), 1222 (m), 1077 (m), 1012 (w), 971 (w), 931 (m), 821 (m), 760 (m) (see Figure S2 of the Supporting Information). Selected IR peaks (cm−1) for 5: 3107 (m), 1619 (w), 1554 (s), 1509 (w), 1364 (s), 1257 (s), 1222 (m), 1077 (m), 1017 (m), 961 (m), 826 (m), 795 (m), 765 (m), 705 (m) (see Figure S2 of the Supporting Information). Syntheses of the Co(tib)(LS)·2H2O (6) and Cd(tib)(LS)·3H2O (7). With H2LS ligands instead of H4L ligands in compounds 1 and 2, 6 and 7 were obtained at 160 °C for three days. The resulting red-bulk crystals of 6 and colorless needlelike crystals of 7 were collected by filtration and washed with H2O several times. Yield: ∼50% (based on

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RESULTS AND DISCUSSION Synthesis and General Characterization. In this work, we focus on constructing interesting target topological networks based on rigid tripodal tib ligand and auxiliary polycarboxylate linkers (H4L, H4LO, and H2LS) by hydrothermal technology with Co2+ or Cd2+ ions. It is worth noting that each complex shows original or extremely rare topologies. The simultaneous employments of tib ligand and polycarboxylates not only contribute to the formation of higher-connected and novel topologies but also make it easier to achieve rational assembly. Such strategy with mixed ligands has been proven to be effective and powerful for development, design, and synthesis of desired metal−organic frameworks (MOFs).7,15 Finally, complexes 1−7 were isolated in good yields. The measured PXRD patterns of all compounds are in good agreement with the simulated patterns generated from the results of single-crystal diffraction data, confirming the phase purity of as-synthesized products (Figure S1 of the Supporting Information). Compounds 1 and 2 are isostructural and crystallize in a monoclinic space group P21/c based upon the analyses of single crystal X-ray diffractions. Taking compound 1 as an example, the asymmetric unit contains one Co2+, one carboxylic ligand, one tib ligand, two aqua ligands, and one lattice water molecule. As depicted in Figure 1, the Co atom is six-coordinated in a distorted octahedral geometry by one oxygen atom from one carboxylate group with a Co−O distance of 2.0928(16) Å, three nitrogen atoms from three tib ligands with Co−N distances ranging from 2.0967(19) Å to 2.142(2) Å, and two aqua ligands with Co−O distances (Table 2). One unique carboxylate ligand is doubly protonated. The carboxylate O(3) and O(6) atoms are most likely protonated as indicated by much-longer C−O bonds [C(29)−O(3): 1.297(3) Å; C(30)−O(6), 1.294(3) Å], compared with the others. It is unidentate and links one Co2+ ion by an O(1) atom, whereas the other oxygen atoms are not 149

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Table 2. Selected Bond Lengths for 1−7a compound 1 Co(1)−O(1) Co(1)−N(6)b Co(1)-O(1W) compound 2 Cd(1)−O(1) Cd(1)−N(6)b Cd(1)-O(1W) compound 3 Co(1)−O(4) Co(1)−N(2) Co(1)−N(10)b Co(2)−O(13) Co(2)−N(12) Co(2)−N(4)c compound 4 Cd(1)−O(4) Cd(1)−N(2) Cd(1)−N(12)b Cd(2)−O(13) Cd(2)−N(4) Cd(2)−N(6)c compound 5 Co(1)−O(2) Co(1)−N(2) Co(2)−O(8)d Co(2)−O(7)f compound 6 Co(1)−O(2) Co(1)−N(2) Co(1)−N(4)d compound 7 Cd(1)−O(1) Cd(1)−O(3)d Cd(1)−N(2) Cd(1)−N(6)c

(2D) layer (Figure 2), in which metal polyhedra are linked into large Co4 rings by four tib ligands and small Co2 rings by a pair

2.0928(16) 2.132(2) 2.1664(17)

Co(1)−N(2) Co(1)−N(4)c Co(1)-O(2W)

2.0967(19) 2.142(2) 2.1545(17)

2.253(3) 2.290(3) 2.381(3)

Cd(1)−N(1) Cd(1)−N(4)c Cd(1)-O(2W)

2.243(3) 2.344(3) 2.408(3)

2.214(2) 2.077(3) 2.106(3) 2.236(2) 2.111(3) 2.089(3)

Co(1)−O(5) Co(1)−N(8) Co(1)-O(1W) Co(2)−O(14) Co(2)−N(6) Co(2)-O(2W)

2.213(2) 2.119(3) 2.118(2) 2.195(2) 2.105(3) 2.140(2)

2.497(4) 2.304(5) 2.263(4) 2.505(4) 2.265(4) 2.283(5)

Cd(1)−O(5) Cd(1)−N(8) Cd(1)-O(1W) Cd(2)−O(14) Cd(2)−N(10) Cd(2)-O(2W)

2.325(4) 2.248(4) 2.314(4) 2.322(4) 2.273(5) 2.296(4)

1.952(2) 1.997(3) 1.995(2) 2.029(2)

Co(1)−O(4)b Co(1)−N(6)c Co(2)−O(6)e Co(2)−N(4)

1.956(2) 2.002(3) 2.016(2) 2.018(3)

2.019(3) 2.101(3) 2.097(4)

Co(1)−O(4)c Co(1)−N(6)b

2.087(3) 2.082(3)

2.525(4) 2.475(4) 2.294(4) 2.320(4)

Cd(1)−O(2) Cd(1)−O(4)d Cd(1)−N(4)b

2.470(4) 2.448(4) 2.292(4)

Figure 2. 2D Co-tib layer parallel to the bc plane in compound 1. CoO3N3 polyhedra are shaded in turquoise. Tib ligands are shown as violet sticks. Free water molecules and hydrogen atoms are omitted for clarity.

of tib ligands. Four-member large rings and two-member small rings alternately connected each other together. The protonated carboxylate ligands coordinate to metal polyhedra filling into the large rings. There are four hydrogen bonds among protonated carboxylate oxygen atoms [O(3) and O(6)], coordinated water molecules [O(1W) and O(2W)], and noncoordination carboxylate oxygens [O(2) and O(8)] with hydrogen bond distances ranging from 2.557(3) to 2.765(3) Å (Figure S3a of the Supporting Information). Such layers are further interlinked into a 3D supramolecular network via hydrogen bonds (Figure S3b of the Supporting Information). When considering the H-bond interaction [O(3)−H(3A)··· O(8), symmetry code: −x + 2, y + 1/2, −z + 1/2], the 3D architecture represents a new (3,4)-connected 2-nodal net (with the Schläfli symbol {4.82.103}{4.82}) from a topological perspective (Figure 3), in which H4L ligands connect the metal centers of adjacent layers by the hydrogen bond between protonated carboxylate oxygen atom [O(3)] and noncoordinated oxygen atom [O(8)], so {H2L}2− anions act as 2connected nodes and are transformed into edges between metal centers during simplification. The tib ligand acts as a 3connected node.

a

Symmetry transformations used to generate equivalent atoms. bFor #1: 1, x, −y + 3/2, z − 1/2; 2, x, −y + 1/2, z − 1/2; 3, −x + 5/2, y + 1/2, −z + 3/2; 4, −x + 1/2, y + 1/2, −z + 3/2; 5, −x + 1, −y + 2, −z + 1; 6, x + 1/2, −y + 2, z; 7, −x + 3/2, −y, z + 1/2. cFor #2: 1, −x + 1, −y + 2, −z + 1; 2, −x + 1, −y + 1, −z + 1; 3, −x + 3/2, y − 1/2, −z + 3/2; 4, −x + 3/2, y − 1/2, −z + 3/2; 5, x, y + 1, z; 6, x − 1/2, −y + 2, z; 7, x, −y + 1/2, z + 1/2. dFor #3: 5, −x + 2, −y + 2, −z; 6, −x + 3/2, y + 1, z − 1/2; 7, x − 1, y, z. eFor #4: 5, −x + 1, −y + 2, −z. fFor #5: 5, x + 1, y − 1, z. gFor #6: 1, −x + 2, y + 1/2, −z + 1/2.

Figure 1. ORTEP representation of the asymmetric unit of 1. Thermal ellipsoids are drawn at the 50% probability level.

involved in metal coordination (Figure 1). The tib ligand is tridentate and links metal centers forming a two-dimensional

Figure 3. View of the simplified network of 1. 150

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for {H2LO}2− (2)], as indicated by the much longer C−O bonds [C(43)−O(2), 1.315(4) Å; C(46)−O(8), 1.282(4) Å; C(59)−O(11), 1.304(4) Å; C(62)−O(17), 1.281(4) Å], compared with the others. Each {H2LO}2− is bidentate and chelates one Co(II) ion by two oxygen atoms of one carboxylate group. The uncoordinated carboxylate O atoms [O(12) and O(15)] H-bond to the coordinated water molecules [O(1W) and O(2W) [O(1W)−H···O(12): 2.780(3) Å (symmetry code: x + 1/2, −y + 1/2, z + 1/2); O(2W)−H···O(15): 2.818(3) Å (symmetry code: x − 1/2, −y + 1/2, z + 1/2)] (Figure S4a of the Supporting Information), which further assembled these layers into a 3D supramolecular structure and directed the formation of a new network (Figure S4b of the Supporting Information). Topologically, each tib acts as planar 3-connected node, and each Co2+ ion acts as 4connecting nodes (nonplanar), to generate a (3,3,4,4)connected 2-nodal network [INIQUR (MOF.ttd)] (Figure 6). The extended Schläfli symbol for this network is {4.6.8}{4.62.83}.

While V-shaped bridging carboxylate ligand (H4LO) with the bent angle [C(45)−O(1)−C(43): 137.07(1)°] replaces the linear H4L ligand, compounds 3 and 4 [M2(tib)2(H2LO)2(H2O)2] (M = Co, 3; Cd, 4) were obtained. They are also isostructural and crystallize in the monoclinic space group P21/n (Figure 4). So the following discussions on

Figure 4. ORTEP representation of the asymmetric unit of 3. Thermal ellipsoids are drawn at the 50% probability level.

the structural descriptions will be mainly focused on 3. There are two crystallographically independent Co atoms, two tib ligands, two protonated carboxylate ligands, and two aqua ligands in its asymmetric unit. Each Co2+ ion is coordinated by two carboxylate oxygen atoms from one H4LO ligand, three N atoms from different tib ligands, and one aqua ligand. The Co− O and Co−N lengths are 2.118(2)−2.236(2) Å and 2.077(3)− 2.119(3) Å, respectively. Metal centers are linked into a 2D layer by two types of tridentate tib along the ab plane with large channels, as depicted in Figure 5, in which the adjacent Figure 6. View of the simplified net along the b-axis of 3. Metal and tib nodes are shown as green and lavender sticks, respectively.

Changing pH value from 3.0 (in 3 and 4) to 6.7 by the addition of 1 M NaOH, compound 5 [Co2(tib)(LO)·H2O] was obtained with a 3D framework different from 2D layers in compounds 3 and 4. The asymmetric unit consists of two crystallographically independent Co atoms, one tib ligand, one deprotonated {LO}4− ligand, and a free water molecule (Figure 7). The local coordination geometry around the Co(1) center

Figure 5. View of the Co-tib layer of 3, in which tib(1) and tib (2) ligands are shown as lavender and violet, respectively. Co atoms are shaded in turquoise balls.

mononuclear Co unit is connected into a one-dimensional (1D) spiral chain along the [010] direction by each unique tib ligands, as shown in different colors with lavender [tib(1)] and violet [tib(2)]. There are two unique H4LO ligands. Each one is doubly protonated with two singly protonated carboxylate groups [O(2) and O(8) for {H2LO}2− (1), O(11) and O(17)

Figure 7. ORTEP representation of the asymmetric unit of 5. Thermal ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. 151

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adopts a typical tetrahedron. It is coordinated by two oxygen atoms from different {LO}4− ligands and two N atoms of two tib. Co(2) features a tetrahedral geometry with three O atoms from three {LO}4− ligands and one N atom of a tib ligand. The distances of Co−O and Co−N bonds span the range of 1.952(2)−2.029(2) Å and 1.997(3)−2.018(3) Å, respectively. One unique {LO}4− ligand is pentadentate and bridges five Co2+ ions by monodentate oxygen atoms, the other oxygen atoms are noncoordinated. As shown in Figure 8, the

Figure 9. Simplified new 3,4,4,5-connected 4-nodal net. Co, tib, and {LO}4− ligands are simplified into turquoise, violet, and gold nodes, respectively, and the Co-tib and Co-LO bonds are shown in twocolored sticks.

Figure 8. View of the 2D Co-LO layer. Color code: turquoise, Co; red, O. H4LO ligands are shown as gold sticks.

connection between Co2+ ions and {LO}4− anions are constructed into the 2D double-fold-line layers, in which dinuclear Co clusters and 1D Co chains are linked by carboxylate groups and are arranged alternately. Such layers are linked into a 3D framework by 1D metal-tib chains (Figure S5 of the Supporting Information), in which neighboring crystallographically equivalent Co(1) and Co(1A) ions are bridged by two N atoms of a tridentate tib ligand. In comparison with the 2D layers of compounds 3 and 4 with same tib and H4LO ligands by hydrothermal reaction with cobalt(II) salts, such 3D framework of 5 was formed with a higher pH value. Upon the addition of NaOH into the reaction solution, H4LO ligands are fully deprotonated, which not only coordinate more metal ions but also occupy more coordinated sites around each metal center. This confirms that O-donor ligands are preferential to the coordinating metal center than to the N-donor ligands and are able to replace some coordinated sites of N atoms. Then 2D Co-LO layer (Figure 8) in 5 is formed instead of the zero-dimensional (0D) mononuclear Co{H2LO}2− cluster in 3 (Figure S4a of the Supporting Information), whereas the 2D Co-tib layer in 3 (Figure 5) is reduced into a 1D Co-tib chain (Figure S5a of the Supporting Information). TOPOS analysis reveals that the 3D framework of 5 can be rationalized to a 3,4,4,5-connected new net with point symbol of {4.6.83.10}{42.63.8}{43.63.84}{6.82}, where the tib ligand is considered as a three-connected node, each unique metal center and {LO}4− ligand is considered as four-connected and five-connected nodes, respectively, during simplification (Figure 9). The V-shaped dicarboxylate ligand (H2LS) with the more electronegative S atom substitute for four-carboxylate ligand (H4LO); compounds 6 and 7 were obtained with 2-fold interpenetrating network and a similar molecular formula Co(tib)(LS)·2H2O for 6 and Cd(tib)(LS)·3H2O for 7. They display a quite different 3D interpenetrating network. Complex 6 crystallizes in the monoclinic chiral space group Pca21. As shown in Figure 10, its unsymmetrical unit contains one unique Co atom, one tib ligand, and a deprotonated LS ligand. The Co

Figure 10. ORTEP representation of the asymmetric unit of 6. Thermal ellipsoids are drawn at the 50% probability level. Hydrogen atoms and free water molecules are omitted for clarity.

center is five-coordinated by three N atoms of three different tib ligands and two O atoms of two carboxylate groups from two different {LS}2− anions and gives a distorted tetragonalpyramid geometry with the Co−O and Co−N lengths of 2.019(3)−2.087(3) Å and 2.082(3)−2.101(3) Å, respectively. The unique deprotonated {LS}2− anion is bidentate and bridges two Co2+ ions by each unidentate carboxylate group; as a result, 1D spiral chains are formed between Co centers and {LS}2− anions (Figure 11 and Figure S6a of the Supporting Information). CoO2N3 square pyramids are connected to form a 3D framework with 1D cubic channels along the [001] direction by tridentate tib ligands (Figure 11). The uncoordinated oxygen atoms and organic groups of the {LS}2− anions are orientated toward the channels, meanwhile free lattice water molecules are also located into the channels. A single net with large channels is apt to construct into interpenetrating frameworks inside the void space to stabilize the whole structure. As is expected, a new Co-MOF 6 with a 2fold interpenetrating framework was obtained (Figure S6b of the Supporting Information). The independent nets in 6 are related by a single vector with a translation vector of [0,1,0] (9.8 Å). In the doubly interpenetration of 6, the metal centers and tib ligands can be regarded as 3-connected nodes; 152

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Figure 13. ORTEP representation of the asymmetric unit of 7. Thermal ellipsoids are drawn at the 50% probability level. Hydrogen atoms and free water molecules are omitted for clarity. Figure 11. One independent single net in the interpenetrating framework of 6 along the c axis. The tib ligands are shown as violet sticks.

direction (Figure S7a of the Supporting Information). Each tridentate tib ligand is coordinated to three Cd2+ ions to expand in crystallographic b- and c-axes to form (3,6)-connected 2D layers (Figure S7b of the Supporting Information). In the 2D layer, three Cd centers and three tib are connected into a hexagonal ring with a diameter of ca. 13.3 Å (including van der Waals radii). The adjacent layers are arranged in a staggered fashion, thus the hexagonal window is divided by the tib ligands from neighboring sheet into three parts along the [100] direction (Figure S7c of the Supporting Information). The separation of adjacent layers is 5.37 Å (a/2). Such layers are arranged into a 3D open framework by extended LS linkers. The 3D framework is opened enough to allow interpenetration. To fully understand the network of the structure of 7, the topological approach is applied to simplify such a 3D coordination framework. Apparently, each Cd center is connected by three tib ligands and two axial carboxylate groups from two LS linkers in opposite orientations, so the metal center is considered as a scarce 5-connected node (Figure 14a). The tib ligands act as 3-connected nodes, and the {LS}2− anions act as the connective pillars between the Cd polyhedra. On the basis of this simplification, this 3D framework can be simplified as a rare binodal (3,5)-connected hms topological network with the point symbol of {63}{69.8} (Figure 14b). What is particularly noteworthy is such a (3,5)-connected net is very limited and only observed in several compounds so far compared to other networks,16 such as the most common 4and 6-connected networks. Effect of Organic Ligand. With several factors in design and syntheses of the metal−organic frameworks taken into consideration, judicious choice of organic ligands is a key strategy. Herein, based on tridentate N-donor tib ligands, three carboxylate ligands (H4L, H4LO, and H2LS) were selected with the different angles of two carboxylate groups from linear to Vshaped and from aromatic polycarboxylate to heteroatomic dicarboxylate ligand. Further, delocalization from ligands H4L to H2LS with their lone pair of electrons gradually increased, carboxylate groups are more easily deprotonated; as a result, more carboxylate oxygen atoms coordinated to the metal center and occupy more sites around metal centers. To the best of our knowledge, O-donor ligands exhibit stronger coordinative abilities of N-donor ligands, as reported, therefore, comparing with 3-connected tib ligands, polycarboxylate ligands showed a

therefore, the whole structure can be represented as a {3.72}{32.75.83}-(3,5)-connected 2-nodal fsf/polar net (Figure 12). The 2-connected {LS}2− anions do not participate in the formation of the 3D framework; they are omitted during simplification.

Figure 12. View of the simplified 2-fold interpenetrating networks along the [010] direction.

Different from compound 6, X-ray crystallography reveals that compound 7 [Cd(tib)(LS)·3H2O] crystallized in centrosymmetric space group Pbca, although it was also synthesized under similar hydrothermal synthesis. Compound 7 shows an interesting and scarce 2-fold interpenetrated (3,5)-connected hms net. The asymmetric unit of 7 contains one Cd2+ ion, one tib ligand, and one {LS}2− anion. The coordination environment around the Cd2+ center of 7 is represented in Figure 13. It is seven-coordinated by four oxygen atoms of two LS ligands [Cd−O = 2.470(4)−2.525(4) Å], three N atoms of three different tib ligands [Cd−N = 2.470(4)−2.525(4) Å], and they furnish a pentagonal bipyramid coordination geometry. Each carboxylate group of one independent LS ligand exhibit μ2coordination modes to chelate one Cd2+ ion. Obviously, each {LS}2− anion is quadridentate and bridges two Cd2+ ions together to form a 1D linear alternating chain along the [100] 153

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H4LO, and H2LS) were also recorded under similar conditions. The tib ligands display photoluminescence with emission maxima at 349 nm (λex = 277 nm), which can be assigned to π*→π transitions. The free linear tetracarboxylic acid (H4L) displays a strong broad fluorescent emission band at λmax = 397 nm under excitation at 337 nm. Upon their complexion with Cd2+ ions, 2 exhibits a much broader fluorescence emission band at λmax = 352 nm (λex = 240 nm). The free V-shaped tetracarboxylate ligands H4LO (λex = 280 nm) can also display photoluminescent peak with a maximum at 343 nm. Compound 4 exhibits one stronger wide band with a maximum at 398 nm and a weak shoulder peak at 296 nm (λex = 249 nm). In comparison with the free tib and H4LO ligands, a small red shift (λmax= 398 nm) and a slightly blue shift (λmax= 296 nm) in compound 4 were observed, which are probably due to enhanced conjugation and asymmetry in the ligands upon metal coordination. When excited with λex = 247 nm, free dicarboxylate ligands (H2LS) give a strong fluorescent emission at 395 nm and two weak peaks at 296 and 339 nm. Cadmium compound 7 shows a broad emission centered at 352 nm (λex = 240 nm). To the best of our knowledge, these emissions are neither metal-to-ligand charge transfer nor ligand-to-metal charge transfer, according to the literature about Cd-coordinated polymers, for it is difficult to oxidize or reduce Cd2+ because of its d10 electronic configuration.17 They can be assigned to the intraligand and ligand-to-ligand charge transition. Thermal Analyses. The thermogravimetric analyses of all compounds under air atmosphere with a heating rate of 10 °C/ min were investigated in the temperature range of 40−800 °C, and TG curves are shown in Figure S9 of the Supporting Information. The TGA curve of 1 displays a first weight loss of 7.54% at 64−114 °C, corresponding to the loss of one free water molecule and two coordinated water molecules. The dehydrated framework is stable to 276 °C, and then the framework begins to collapse, accompanying the release of organic ligands (tib and H4L). The total weight loss at 441 °C is 88.3%. For compound 3, a minor weight loss of two coordinated water molecules (found, 2.52%; calcd, 2.58%) occurred from 94 to 189 °C. Then a gradual weight loss in the temperature range of 269−469 °C corresponds to the combustion of organic ligands, and the total weight loss is 87.8%. As shown in Figure S9 of the Supporting Information, the TGA result of 5 reveals a contant weight loss of 2.18% before 132 °C, which is abscribed to the removel of one free water molecule (2.38%). Then the framework collapsed till 317 °C. For 6, the first step (58−174 °C) exhibits one continuous weight loss, which corresponds to the release of two free water molecules (found, 6.2%; calcd, 6.6%). After that, it starts to decompose at 285 °C, and the total weight loss is 88.7% at 497 °C. TGA curves of three Cd-MOFs (2, 4, and 7) are similar to their isostructural Co-MOFs, so their thermogravimetric analyses are shown in Figure S9 of the Supporting Information. Magnetic Property Measurements. In all Co-MOFs (1, 3, 5, and 7) obtained, complexes 1, 3, and 7 display isolated mononuclear clusters; only compound 5 contains 1D regular alternating chains, so it may be easily envisaged as exhibiting interesting magnetic behavior, especially since the magnetic behavior for the Co2+ complexes is rather complicated and unexpected because of its spin−orbital coupling, as known. Therefore, the temperature dependence of magnetic susceptibility of only compound 5 was investigated in the temperature range of 2−300 K at an applied magnetic field of 1000 Oe. Yet,

Figure 14. View of (a) one independent single net and the (b) simplified hms net of 7. Color code: in (a) Cd and O atoms are shaded in green and red balls, respectively.

higher variety of coordination modes with different orientations, which results in the different structural motifs and topologies. Upon further structural analysis, aforementioned considerations have also been further verified. From the structure description above, we noticed that tib ligands are coordinated to metal centers by three N atoms to easily form 2D metal-tib layers in most cases (compounds 1 and 2, 3 and 4, and 7) based on similar reaction conditions. H4L and H4LO ligands in 1−4 are protonated and link metal centers into mononuclear clusters, so it does not participate in the construction of 3D but form hydrogen-bonded 3D structures, whereas H2LS ligands are fully deprotonated and connect metal centers to the 1D chain, as opposite axial pillared into 3D open framework with rare binodal (3,5)-connected fsf/polar net for 6 and (3,5)connected hms net for 7. After an adjustment of the pH of the reaction to 6.7, the H4LO ligand in 5 became fully deprotonated and took the place of some coordination sites around the metal centers to the 2D metal-LO layer; as a result, the 2D metal-tib layer in 3 is reduced into a 1D metal-tib chain, which further confirms our original synthetic strategy. Luminescence Properties. In consideration that metal complexes with a d10 electronic configuration usually exhibit excellent luminescent properties, the solid-state photoluminescence spectra of complexes 2, 4, and 7 were investigated at room temperature, as depicted in Figure S8 of the Supporting Information. For comparison, the luminescence properties of free tib ligand and three different carboxylate ligands (H4L, 154

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χM−1 for 5. This material is available free of charge via the Internet at http://pubs.acs.org.

it only shows an ordinary antiferromagnetic feature. For 5, the χM and χMT versus T plots are shown in Figure S10 of the Supporting Information. The χMT value at 300 K is 5.48 cm3 mol−1 K. Along with the lowering temperature, the χMT value decreases slowly and then more rapidly below 76 K to reach the value of 1.33 cm3 mol−1 K at 2 K. The reciprocal molar magnetic susceptibility versus temperature obeys the Curie− Weiss law in the temperature range of 2−300 K with a Weiss constant of (θ) −15.0 K and the Curie constant of C = 5.67 cm3 mol−1 K, which is much higher than the expected value for two uncoupled Co2+ ions with g = 2 and S = 3/2 (3.74 cm3 mol−1 K), ascribing to the spin−orbit effect of Co(II) ions. The negative Weiss constant suggests that the dominant interation between spin carriers is antiferromagnetic and can be shown as the decrease in χMT value when T decreases. After the combination of the structure data of compound 5, two Co(1) atoms are bridged into dinuclear Co(1)II2 units by one type of Co−O−C−C−C−C−O−Co magnetic exchange pathway; Co(2) atoms are bridged into 1D Co(2)−LO chain by Co− O−C−C−C−C−O−Co bridge and Co−O−C−O−Co bridge in its 2D Co−LO layer (Figure 8, S10a of the Supporting Information). Omitting the very weak interaction between two Co centers bridged by Co−O−C−C−C−C−O−Co, the magnetic data can be fitted by the following equation, which is deduced from the spin Hamiltonian on the basis of an approximate model of dinuclear Co(II) units bridged by carboxylate ligands.18

■

*E-mail: [email protected]. Author Contributions §

H.W. and F.-Y.Y. contributed equally.

Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We thank NSFC for the support of this work (Grants 21101148, 21171662, and 21201162), SRF for ROCS (State Education Ministry), and Jilin Province Youth Foundation (Grants 20130522132JH, 20130522170JH, and 201201005).

■

=

Ng 2β 2 84e12J / kT + 30e 6J / kT + 6e 2J / kT × 12J / kT 3kT 7e + 5e 6J / kT + 3e 2J / kT + 1

2Ng 2β 2 14e12J / kT + 5e 6J / kT + e 2J / kT × 12J / kT kT 7e + 5e 6J / kT + 3e 2J / kT + 1

χM =

(1)

χt 1 − (2zJ ′/Ng 2β 2)χt

(2)

In eqs 1 and 2, N, g, β, kB, and T have their usual meanings. The best fit gives J/kB = −4.64 K, zJ′/kB = −1.34 K, and g = 2.28. These data further confirm the antiferromagnetic interation between the neighboring Co(II) ions. The nature of the curves and magnitude of the exchange parameters are consistent with the previously reported Co(II) compounds bridged by Vshaped carboxylate ligands.19 In conclusion, seven new Co(II)/Cd(II)-MOFs constructed from a tridentate tib ligand and different polycarboxylates selected have been successfully obtained under hydrothermal conditions. They feature unusual or rare networks from (3,4)-c for 1 and 2, (3,3,4,4)-c for 3 and 4, (3,4,4,5)-c for 5, to (3,5)-c fsf/polar net for 6 and hms net for 7. The results indicate that introduction of predesigned polycarboxylate ligands with different twisted angle and electronegativity is significantly effective on the formations of the desired topological networks. The dual-ligand method utilizing synergistic effects also plays an important role in the construction of novel topologic nets.

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Ĥ = −2J S1̂ Ŝ2 χt =

AUTHOR INFORMATION

Corresponding Author

ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic cif files, simulated and measured XRD patterns, structural figures, solid-state emission spectra, IR data, TGA curves of 1−7, and temperature dependence of χMT and 155

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dx.doi.org/10.1021/cg4013334 | Cryst. Growth Des. 2014, 14, 147−156