CadmiumâFurandicarboxylate Coordination Polymers Prepared with

Article pubs.acs.org/crystal

Cadmium−Furandicarboxylate Coordination Polymers Prepared with Different Types of Pyridyl Linkers: Synthesis, Divergent Dimensionalities, and Luminescence Study Rupam Sen,*,† Dasarath Mal,† Paula Brandaõ ,† Rute A. S. Ferreira,‡ and Zhi Lin*,† †

Department of Chemistry, CICECO, University of Aveiro, 3810-193, Aveiro, Portugal Department of Physics, CICECO, University of Aveiro, 3810-193, Aveiro, Portugal

‡

S Supporting Information *

ABSTRACT: Five new metal−organic frameworks (MOFs) have been synthesized by using cadmium ion and 2,5-furandicarboxylic acid in presence of a variety of bridging amine ligands, [Cd(fdc)(2,2′-bpy)(H2O)]n (1), {[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2), {[Cd(fdc)(4,4′-bpy)(H2O)2]·EtOH}n (3), [Cd(fdc)(1,2-bpe)(H2O)]n (4), and [{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5), where fdc = 2,5-furandicarboxylic acid, 2,2′-bpy = 2,2′-bipyridyl, pyz = pyrazine, 4,4′-bpy = 4,4′-bipyridyl, 1,2-bpe = 1,2-di(4-pyridyl)ethylene. All the compounds were characterized by singlecrystal X-ray analysis and show diversities in their structures. Compound 1 shows linear topology propagating along the crystallographic b-axis. Compound 2 shows supramolecular structure, where two types of 1D double chains (ladder type) are present. These chains propagate along the crystallographic a-axis and are tightly held with each other by strong hydrogen bonds. Compound 3 reveals a 1D + 1D → 2D polycatenated MOF, where four cadmium centers form a perfect square and these squares are further linked by the carboxylate ligand, forming a 1D tube. These tubes are interpenetrated with each other forming a polycatenated 3D MOF. Compound 4 also possesses a polycatenated MOF, but 1D sheets are polycatenated with each other forming the 1D + 1D → 3D MOF. Compound 5 is a 2D-based supramolecular 3D MOF, where 1,2-bpe ligands are entrapped within the layer of the 2D by strong hydrogen bonds and π···π interaction. Luminescence of all the compounds has been investigated.

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INTRODUCTION A rapid expansion has been realized in the synthesis and application of metal−organic frameworks (MOFs) during the past decade. Immense attention on MOFs arises not only for their fascinating capability to form a variety of architectures and topologies but also for their potential applications such as in catalytic reactions,1 gas adsorption and separation processes,2 and molecular magnetism3 and also as luminescent materials.4 However, it has always been a challenge to produce desired MOF materials with controlled properties. Obtaining the desired architectures of MOFs designed by specific organic ligands and metal ions is a very complicated and difficult process that depends on many parameters, such as auxiliary ligands, pH of the medium, reaction temperature, and reactant ratio, which have vital impact on the structure and topology of the resulting frameworks. But a careful synthetic approach may produce desirable MOFs with different dimensionalities and properties.5 Moreover, molecular self-assembly processes and isoreticular synthesis have now guided us to develop the field of supramolecular chemistry6 and crystal engineering7 to find novel multifunctional MOF materials. Isoreticular synthesis, which is the classical approach to the design and assembly of targeted MOFs, involves the linking of simple, structuredirecting geometric small units called secondary building units (SBUs) by organic linkers into the desired framework topology. © XXXX American Chemical Society

Isoreticular synthesis has explained the assembly process of predesigned MOFs in a logical and straightforward manner and the ability to tune the size and functionality of MOFs without disturbing the overall structure. To synthesize the MOFs, the use of molecular building blocks that have some structural guidance toward self-assembling processes is the key issue in this process. Recently, much effort has been devoted to the rational design and controlled synthesis of coordination polymers using multidentate ligands. Among the different connecting ligands, aliphatic and aromatic carboxylic acids (mono, di, tri, tetra, etc.) are the most deserving candidates evolving a large class of desired MOFs. Notably, carboxylates have versatile bridging modes; they can act as monodentate, bidentate, and even more.8,9 Because of their variable modes of syn−syn, syn−anti and anti−anti, they can control the topology and the properties of the MOFs. Moreover, the bridging carboxylate ligands can be functionalized and also postsynthetically modified quite easily. Framework materials with the carboxylate have a wide range of variety from rigid to flexible. One can tune the structure by introducing desired ligands according to the demand of properties. It is worth mentioning Received: July 9, 2013 Revised: October 14, 2013

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dx.doi.org/10.1021/cg401036e | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

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Table 1. Crystal Data and Structure Refinement Parameters for Complexes 1−5 formula formula wt temp (K) wavelength (Å) cryst. syst. space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) vol (Å3) Z calcd density (Mg/m3) abs coeff (mm−1) F(000) θ range for data collection (deg) final R indices [I > 2σ(I)] GOF on F2 largest diff. peak and hole (e Å−3)

1

2

3

4

5

C16H12N2O6Cd 440.69 288(2) 0.71073 monoclinic Pc 7.8256(4) 10.0204(5) 20.8235(9) (90) 90.102(2) (90) 1632.89(14) 4 1.793 1.373 872 2.60, −27.99 0.0251, 0.0493 1.054 0.670, −0.306

C14H16NO15Cd2 663.08 180(2) 0.71073 monoclinic P21/n 9.9478(3) 10.9061(3) 18.6373(6) (90) 103.2360(10) (90) 1968.28(10) 4 2.238 2.243 1292 2.25, −33.24 0.0243, 0.0486 1.028 0.846, −0.474

C34H25N4O13Cd2 927.42 180(2) 0.71073 triclinic P1̅ 9.9344(6) 11.6032(6) 16.4640(10) 76.643(3) 82.486(3) 75.074(2) 1779.05(18) 2 1.731 1.267 924 2.40, −30.59 0.0370, 0.0754 1.098 1.338, −0.496

C30H25N3O13Cd2 860.33 180(2) 0.71073 monoclinic P21/n 9.8908(7) 14.3305(10) 21.8335(14) (90) 95.183(2) (90) 3082.0(4) 4 1.854 1.454 1704 2.35, −28.35 0.0418, 0.0871 1.117 1.553, −1.663

C48H36N4O24Cd3 1390.01 150(2) 0.71073 triclinic P1̅ 10.1306(4) 10.1685(4) 11.9873(5) 83.831(2) 78.767(2) 81.005(2) 1192.51(8) 1 1.936 1.423 688 2.07, −30.63 0.0207, 0.0485 1.049 0.832, −0.407

pyrazine, 4,4′-bpy = 4,4′-bipyridyl, 1,2-bpe = 1,2-di(4-pyridyl)ethylene. Depending on the bridging ligands, we have successfully isolated different topological frameworks, from 1D to 3D. Luminescence properties of all the compounds have been studied and discussed.

that MOFs with large pores are of particular interest due to their many applications from catalysis to gas adsorption. It is well reported that bifunctional dicarboxylates served to bridge various metal ions producing many highly porous and catalytically active frameworks.10 Yaghi’s group has developed a family of compounds based on one structural arrangement in which the pore size may be tuned over a wide range. By using longer or shorter organic molecules of similar geometry, Yaghi et al. have now prepared 16 variations on the MOF-5 structure, with pores varying from 3.8 to 28.8 Å in diameter.11 By tuning the porous channel, one can rationalize the adsorption and catalytic properties within the pores of the materials. Recently, we have developed a series of 3D interpenetrated frameworks by using a dicarboxylate and bridging amine ligand.12 It is noteworthy that Cd(II)-containing coordination polymers gained much attention due to their ability to form bonds with different donors simultaneously and the large radius, the various coordination numbers, and the extraordinary physical properties of the Cd(II) ion. Cadmium(II) has been reported in tetrahedral, trigonal bipyramidal, octahedral, distorted pentagonal bipyramidal, and distorted dodecahedral coordination geometries.9g This structural variation in Cd2+ coordination geometry arises from two effects: (i) the large ionic radius of Cd2+ allows flexibility in terms of coordination number, and (ii) the d10 electronic configuration of Cd2+ ions serves to eliminate ligand field effects and thereby permits diverse geometries. To date, researchers have reported a number of frameworks with different dimensionalities. Cd(II) coordination polymers are now highly desired for their prospective applications in catalysis, luminescent materials, NLO materials, phase transformation, and host−guest chemistry.9g−i In continuation of our work, herein we introduce a series of cadmium-based furandicarboxylate frameworks using different bridging amine ligands, [Cd(fdc)(2,2′-bpy)(H2O)]n (1), {[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2), {[Cd(fdc)(4,4′-bpy)(H2O)2]·EtOH}n (3), [Cd(fdc)(1,2-bpe)(H2O)]n (4), and [{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5), where fdc = 2,5-furandicarboxylic acid, 2,2′-bpy = 2,2′-bipyridyl, pyz =

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EXPERIMENTAL SECTION

Materials and Physical Measurements. Cadmium nitrate hexahydrate, fdc, pyz, 4,4′-bpy, 1,2-bpe, and 2,2′-bpy were purchased from Aldrich and were used as received. Fourier transformed infrared spectra of samples suspended in KBr pellets were measured on a Unican Mattson Mod 7000 spectrophotometer equipped with a DTGS CsI detector. Elemental analyses (CHN) were performed using a Perkin−Elmer 240 elemental analyzer. Thermogravimetric analyses (TGA) were carried out using a Shimadzu TGA 50, with a heating rate of 5 °C/min, under a continuous stream of nitrogen with a flow rate of 20 cm3/min. The powder X-ray diffraction (PXRD) patterns of the samples were recorded with a Philips X’Pert MPD diffractometer equipped with an X’Celerator detector. The photoluminescence spectra were recorded at room temperature with a modular double grating excitation spectrofluorimeter with a TRIAX 320 emission monochromator (Fluorolog-3, Horiba Scientific) coupled to an R928 Hamamatsu photomultiplier, using a front face acquisition mode. The excitation source was a 450 W Xe arc lamp. The emission spectra were corrected for detection and optical spectral response of the spectrofluorimeter, and the excitation spectra were corrected for the spectral distribution of the lamp intensity using a photodiode reference detector. X-ray Crystallography. Single crystal X-ray diffraction data of 1− 5 were collected on a Bruker SMART APEX CCD X-ray diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The determination of integrated intensities and cell refinement were performed with the SAINT13 software package using a narrow-frame integration algorithm. An empirical absorption correction (SADABS)14 was applied. All the structures were solved by direct methods and refined using the full-matrix least-squares technique against F2 with anisotropic displacement parameters for non-hydrogen atoms with the programs SHELXS97 and SHELXL97.15 The hydrogen atoms of the C−H bonds were placed at geometrical positions and refined with Uiso = 1.2Ueq of the atom to which they are attached, whereas the hydrogen atoms bonded to water molecules were obtained from the last final difference Fourier maps B



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Table 2. Selected Bond Lengths [Å] and Angles [deg] for Complexes 1−5 bond distances CdA−O1A CdA−O11A CdA−O2A CdA−O3A CdA−O12A CdA−N13A CdA−N24A CdB−O1B CdB−O3B CdB−O12B CdB−O2B CdB−N13B CdB−N24B Cd1−O1 Cd1−O2 Cd1−O4 Cd1−O12 Cd1−O13 Cd1−N14 Cd2−O17 Cd2−O18 Cd2−O19 Cd2−O20 Cd2−O28 Cd2−O29 Cd1−O1 Cd1−O2 Cd1−O3 Cd1−O11 Cd1−O12

bond angles

Compound 1 2.287(3) O1A−CdA−O11A 2.300(2) O1A−CdA−O2A 2.356(2) O11A−CdA−O2A 2.460(2) O1A−CdA−N13A 2.566(2) O11A−CdA−N13A 2.381(3) O1A−CdA−N24A 2.324(3) O2A−CdA−N13A 2.294(2) O1A−CdA−O3A 2.299(2) N13A−CdA−O3A 2.356(2) O1A−CdA−O12A 2.566(2) O11A−CdA−O12A 2.385(2) N24A−CdA−O12A 2.316(3) O2A−CdA−O12A Compound 2 2.2487(13) O1−Cd1−O2 2.2617(14) O1−Cd1−O4 2.2683(12) O2−Cd1−O4 2.4100(12) O1−Cd1−N14 2.4009(13) O2−Cd1−N14 2.3973(15) O4−Cd1−N14 2.2941(14) O1−Cd1−O13 2.2530(15) O2−Cd1−O13 2.4304(13) O4−Cd1−O13 2.3591(12) O18−Cd2−O29 2.2834(13) O18−Cd2−O17 2.2784(14) O17−Cd2−O20 Compound 3 2.312(2) O1−Cd1−O2 2.3810(19) O1−Cd1−O3 2.4312(19) O1−Cd1−O12 2.2991(18) O2−Cd1−O12 2.5164(19) O3−Cd1−O12

bond distances 96.65(9) 92.65(9) 87.74(7) 164.67(9) 98.68(9) 100.84(10) 88.04(9) 84.00(8) 83.93(9) 78.75(8) 53.44(7) 77.37(8) 138.11(7)

Cd2−O13 Cd2−O24 Cd2−O15 Cd2−N34 Cd2−N37 Cd1−O1 Cd1−O2 Cd1−O3 Cd1−O4 Cd1−O12 Cd1−O13 Cd2−O14 Cd2−O15 Cd2−O16 Cd1−N26 Cd2−N37 Cd2−N40

80.98(5) 137.70(5) 88.26(5) 96.36(5) 177.24(5) 94.23(5) 136.19(5) 89.66(5) 84.02(5) 90.38(6) 170.54(6) 87.91(5)

Cd1−O1 Cd1−O2 Cd1−O3 Cd2−O4 Cd2−O12 Cd2−O13 Cd2−O14 Cd2−O23 Cd2−O24 C8−C9 C9−C10 O3−C5

93.24(7) 91.28(7) 92.03(7) 136.84(6) 167.70(6)

bond angles

Compound 3 2.332(2) O11−Cd1−O12 2.2970(19) O13−Cd2−N34 2.353(2) O24−Cd2−O15 2.339(2) O24−Cd2−N37 2.376(2) O13−Cd2−O15 Compound 4 2.411(3) O2−Cd1−O1 2.264(4) O3−Cd1−O1 2.364(3) O2−Cd1−O4 2.480(3) O1−Cd1−O4 2.288(3) O2−Cd1−O3 2.625(3) O2−Cd1−O13 2.268(3) O12−Cd1−O1 2.382(3) O2−Cd1−O12 2.399(3) O12−Cd1−O3 2.323(3) O12−Cd1−N26 2.417(3) N26−Cd1−O1 2.459(4) O2−Cd1−N26 Compound 5 2.2647(12) O1−Cd1−O1 2.2465(11) O2−Cd1−O1 2.3317(11) O2−Cd1−O2 2.2801(11) O1−Cd1−O3 2.3735(12) O2−Cd1−O3 2.3857(11) O3−Cd1−O3 2.1830(11) O14−Cd2−O23 2.2645(12) O14−Cd2−O4 2.5458(12) O23−Cd2−O4 1.358(2) O14−Cd2−O12 1.422(2) O4−Cd2−O12 1.2467(18) O14−Cd2−O13

54.28(6) 84.14(8) 85.03(7) 87.66(8) 105.36(8) 164.33(12) 103.23(11) 101.30(13) 84.91(11) 91.97(12) 88.51(13) 92.97(12) 92.93(14) 81.75(11) 138.18(12) 79.86(11) 86.07(12) 179.999(1) 90.77(4) 180.0 92.35(4) 82.41(4) 179.999(1) 150.36(4) 99.47(4) 89.13(4) 116.48(4) 91.03(4) 98.32(4)

by comparing the PXRD patterns of the bulk sample and simulated one (Figure S3, Supporting Information). Anal. Calcd (%) for C14H16NO15Cd2: C, 25.33; H, 2.41; N, 2.11. Found: C, 25.83; H, 2.68; N, 2.05. Selected IR peaks (KBr disk, ν, cm−1): 1603, 1550 [υas(CO2−)], 1402 [υs(CO2−)], 1349, 1229 [υs(C−O)], and 3600− 3200 s.br [υ(O−H)] (Figure S2, Supporting Information). {[Cd(fdc)(4,4′-bpy)(H2O)2]·EtOH}n (3). Similar synthetic procedure as that for 1 was followed by using Cd(NO3)2·4H2O (154 mg, 0.5 mmol), 4,4′-bpy (78 mg, 0.5 mmol), fdc (78 mg, 0.5 mmol), water (6 mL), and ethanol (2 mL). Colorless X-ray-quality needle crystals of 3 (dimension, 0.20 × 0.04 × 0.01 mm3) were recovered in 68% yield (based on Cd(II)). Phase purity was checked by comparing the PXRD patterns of the bulk sample and simulated one (Figure S4, Supporting Information). Anal. Calcd (%) for C34H26N4O13Cd2: C, 43.99; H, 2.69; N, 6.03. Found: C, 44.51; H, 2.89; N, 6.32. Selected IR peaks (KBr disk, ν, cm−1): 1603, 1576 [υas(CO2−)], 1416 [υs(CO2−)], 1349, 1229 [υs(C−O)], and 3600−3200 s.br [υ(O−H)] (Figure S2, Supporting Information). [Cd(fdc)(1,2-bpe)(H2O)]n (4). The synthetic procedure is similar to that of 3, only replacing 4,4′-bpy with 1,2-bpe, and the temperature is 140 °C. Colorless X-ray-quality needle crystals of 4 (dimension, 0.50 × 0.02 × 0.01 mm3) were obtained. Yield: 40% (based on Cd(II)). Phase purity was checked by comparing the PXRD patterns of the bulk sample and simulated one (Figure S5, Supporting Information). Anal. Calcd (%) for C30H25N3O13Cd2: C, 41.84; H, 2.90; N, 4.88. Found: C, 42.11; H, 3.02; N, 4.97. Selected IR peaks (KBr disk, ν, cm−1): 1602, 1578 [υas(CO2−)], 1430 [υs(CO2−)], 1376, 1229 [υs(C−O)], and 3600−3200 s.br [υ(O−H)] (Figure S2, Supporting Information).

and refined isotropically. For compound 4, the hydrogen atoms bonded to the water molecule (O13) were not discernible from the last final difference Fourrier maps and consequently were not included in the structure refinement. In the final difference Fourier maps, there were no remarkable peaks except the ghost peaks surrounding the metal centers in all the compounds. A summary of crystal data and relevant refinement parameters for compounds 1−5 are given in Table 1. Selected bond distances and angles for compounds 1−5 are listed in Table 2. Synthesis and Preliminary Characterization of the Compounds. [Cd(fdc)(2,2′-bpy)(H2O)]n (1). A mixture containing Cd(NO3)2·4H2O (154 mg, 0.5 mmol), 2,2′-bpy (156 mg, 1.0 mmol), fdc (78 mg, 0.5 mmol), water (6 mL), and ethanol (2 mL) was sealed in a Teflon-lined stainless steel vessel (23 mL), which was heated at 160 °C for 3 days and then cooled to room temperature. Pale colored block crystals of 1 (dimension 0.20 × 0.12 × 0.06 mm3) were obtained, collected, washed with distilled water, and dried in air. Yield: 47% (based on Cd(II)). Phase purity was checked by comparing the PXRD patterns of the bulk sample and a simulated one from the single crystal X-ray data (Figure S1, Supporting Information). Anal. Calcd (%) C16H12N2O6Cd: C, 43.56; H, 2.72; N, 6.35. Found: C, 43.98; H, 2.39; N, 6.78. Selected IR peaks (KBr disk, ν, cm−1): 1643, 1590 [υas(CO2−)], 1470 [υs(CO2−)], 1442, 1376 [υs(C−O)], and 3600− 3200 s.br [υ(O−H)] (Figure S2, Supporting Information). {[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2). The same synthetic procedure as that for 1 was used except here 2,2′-bpy was replaced by pyz and the solvent was only water (10 mL), giving colorless needle X-ray-quality crystals of 2 (dimension, 0.40 × 0.06 × 0.01 mm3) in 40% yield (based on Cd(II)). Phase purity was checked C



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[{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5). Phase pure compound 5 was synthesized at 170 °C. At 150 °C, compounds 4 and 5 both crystallized at the same time, while at 140 °C, we obtained the phase pure compound 4. The rest of the process is similar to the synthesis of 4 by keeping Cd(NO3)2·4H2O (154 mg, 0.5 mmol), fdc (78 mg, 0.5 mmol), 1,2-bpe (91 mg, 0.5 mmol), water (6 mL), and EtOH (2 mL) at 170 °C for 3 days in the autoclave and then cooling to room temperature. Pale colored X-ray quality block shaped single crystals of 5 (dimension, 0.22 × 0.20 × 0.08 mm3) were precipitated. Yield: 52% (based on Cd(II)). Phase purity of the compound was checked by comparing the PXRD patterns of the bulk sample and simulated one (Figure S6, Supporting Information). Anal. Calcd (%) for C48H36N4O24Cd3: C, 41.43; H, 2.58; N, 4.02. Found: C, 41.82; H, 2.71; N, 4.29. Selected IR peaks (KBr disk, ν, cm−1): 1602, 1572 [υas(CO2−)], 1500 [υs(CO2−)], 1408, 1366 [υs(C−O)], and 3600− 3200 s.br [υ(O−H)] (Figure S2, Supporting Information).

MOFs, featuring important photoluminescence properties. More fascinatingly, Cd ions can adopt a variety of coordination numbers from four to seven in common,19 being able to adopt different topological networks. Herein, we intend to modulate the interplay of the different bridging ligands within the same cadmium furandicarboxylate system. As a result, five new coordination polymers have been constructed, and the structural diversities are discussed. Closer observation on the structures of 1−5 clearly reveals that different coordination modes of the O-heterocyclic carboxylate and the different bridging ligands lead them to adopt various different topological structures. Structure Description of [Cd(fdc)(2,2′-bpy)(H2O)]n (1). Compound 1 crystallized in the space group Pc with Z = 4. In the asymmetric unit of compound 1, the metal center is in distorted pentagonal bipyramidal geometry. The basal plane of the central metal ion is formed by the four oxygen atoms from the two chelating fdc ligand and one nitrogen atoms from the chelating bpy ligand (for CdA center O2A, O3A, O11A, O12A, and N24A, respectively). The axial positions are occupied by one water molecule (O1A) and another nitrogen atom of the bpy ligand (N13A). ORTEP diagram with atom numbering scheme has been shown in Figure 1. The Cd−O and Cd−N

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RESULTS AND DISCUSSION Synthesis of the Materials. The N/O-heterocyclic carboxylic acids are very helpful to produce the metal−organic frameworks with diverse dimensionality. In the recent past, a variety of framework systems has been developed by using the N/O-heterocyclic carboxylate ligands. It is also notable that the heterocyclic carboxylic acids are very responsive toward the external stimuli (like temperature, pH, solvent, etc.) to produce different topological frameworks.16,17 In our recent work, we have successfully developed 0D to 3D frameworks by changing only the pH of the medium based on N-heterocyclic carboxylate system.17a Maji et al. synthesized a new series of frameworks in the N-heterocyclic carboxylate system by varying the temperature.17b Recently, Ghosh et al. prepared a series of Zn-based O-heterocyclic carboxylate frameworks with different dimensionalities by tuning the reaction temperature.17c In this study, we have developed a series of Cd-based furandicarboxylates by varying the bridging amine ligands. Here, the Oheterocylic carboxylate also shows a different bridging mode to successfully construct the different molecular frameworks (Scheme 1). It is worth mentioning that the deliberate use of

Figure 1. ORTEP diagram of compound 1 with 30% ellipsoid probability.

bond distances are in the range of 2.287(3)−2.566(2) and 2.316(3)−2.385(2) Å, respectively, which are in well agreement with the previously published works.19 These centers are connected with each other in a double chelating fashion by the fdc ligand forming a linear 1D infinite chain parallel to the crystallographic b-axis (Figure 2). In the crystal packing, these chains are strongly bonded with each other by the hydrogen bonding mediated through the coordinated water molecules and form supramolecular network in the crystallographic 3D space as O(1A)−H(1A)···O(12B) [x − 1, y, z], O(1B)− H(1B)···O(2A) [x, y − 1, z], O(1A)−H(2A)···O(3B) [x − 1, y + 1, z], O(1B)−H(2B)···O(11A) (Table S1, Supporting Information). Structure Description of {[Cd(fdc)(pyz)(H2O)2][Cd(fdc)](H2O)2]·H2O}n (2). Compound 2 crystallized in the space group P21/n with Z = 4. The asymmetric unit is formed by the two discrete one-dimensional part along with one crystallographic water molecule. Both parts possess ladder type chain structure (see ORTEP diagram, Figure 3). The first part is formed by Cd1, fdc, and bridging pyz ligands (Figures 3 and 4), while the second part is exclusively formed by another Cd2 ion and fdc ligand (Figures 3 and 5). In both parts, Cd ions are in distorted pentagonal bipyramid geometry. In part one, the basal plane of the pentagonal bipyramid is formed by four oxygen atoms from the two chelating fdc ligands (O3, O4, O12, and O13) and one water molecule (O1) and the axial positions

Scheme 1. Bridging Modes of fdc Ligand Present in (i) Compounds 1, 2, 3, and 4, (ii, iii) Compound 5, and (iv) Compound 2

N-donor auxiliary ligands with the carboxylate ligands is also an effective method for designing and constructing coordination complexes. For example, 4,4′-bpy and its flexible derivative 1,2bpe show a great influence on the assembly process and have been extensively used in the construction of a variety of MOFs with different metal centers.12,18 The application of these bridging N-donor ligands in MOF synthesis often results in exceptional structures with unique motifs and useful functional properties. Furthermore, it is notable that Cd has attracted extensive interest as metal centers for the construction of D



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Figure 2. One-dimensional chain of compound 1, propagating parallel to the crystallographic b-axis.

Figure 5. Ladder structure of part two in compound 2: (c) molecular structure; (d) model structure of the ladder.

graphic a-axis (Figure 5). In the structure, these two parts are bonded with each other through strong intra- and intermolecular hydrogen bonding interactions including multiple O− H···O hydrogen bonds (Table S1, Supporting Information), O(1)−H(1A)···O(17) [x, y − 1, z], O(1)−H(1A)···O(20) [x, y − 1, z], O(1)−H(1B)···O(20) [−x, −y + 1, −z], O(2)− H(2A)···O(4) [−x + 1/2, y − 1/2, −z + 1/2], O(2)−H(2B)··· O(19) [−x + 1/2, y − 1/2, −z + 1/2], O(17)−H(17A)··· O(13) [−x + 3/2, y + 1/2, −z + 1/2], O(17)−H(17B)···O(3) [x, y + 1, z], O(18)−H(18A)···O(3) [−x + 1, −y + 1, −z], O(18)−H(18A)···O(7) [−x + 1, −y + 1, −z], O(18)− H(18B)···O(7) [−x + 1, −y + 1, −z], O(18)−H(18B)···O(12) [−x + 1, −y + 1, −z], forming a supramoleculer 3D network. Structure Description of {[Cd(fdc)(4,4′-bpy)(H2O)2]· EtOH}n (3). Compound 3 crystallized in the space group P1̅ with Z = 4 and reveals a polycatenated MOF along with an ethanol molecule in the crystal lattice. Here, both Cd centers are in pentagonal bipyramidal geometry. The basal plane is formed by the four chelating oxygen atoms (O14, O15, O23, and O24) from the two different fdc ligands, and remaining one is occupied by one nitrogen atom of the bridging 4,4′-bpy ligand (N34); the axial positions are filled with one water molecule (O13) and one nitrogen atom from another bridging 4,4′-bpy ligand (N37) (see ORTEP structure, Figure 6). The Cd−O and Cd−N bond distances are in good agreement with the previously reported works.19 These Cd centers are connected alternatively by the bridging bpy ligand forming a

Figure 3. ORTEP diagram of compound 2 with 30% ellipsoid probability, symmetry operation codes, i = −x, 1 − y, −z; ii = 1 − x, 1 − y, −z; iii = −x, 2 − y, −z; iv = 1 + x, y, z; v = −1 − x, 2 − y, −z.

are occupied by one water molecule (O2) and one nitrogen atom from the bridging pyz ligand (N14). The Cd−O and Cd− N bond distances are in well agreement with the previously reported works.19 These centers are connected with each other in a double chelating fashion (see Scheme 1, image i) by the fdc ligand forming a linear 1D infinite chain parallel to the crystallographic a-axis. These chains are further connected with each other by the bridging pyz ligand forming the final ladder type structure (Figure 4). On the other hand, in part two the basal plane of the pentagonal bipyramid is formed by four chelating oxygen atoms from the two fdc ligands (O19, O20, O28, O29) and one μ2-O (O29*, * = 1 + x, y, z) from another fdc ligand, and the axial positions are occupied by the two water molecules (O17 and O18). These centers are connected with each other (Scheme 1, image iv) by the fdc ligand forming a linear 1D infinite ladder type chain parallel to the crystallo-

Figure 4. Ladder structure of part one in compound 2: (a) molecular structure; (b) model structure of the ladder. E



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Figure 8. The simplified form of topological polycatenation among the 1D porous tubes present in compound 3.

Figure 6. ORTEP diagram of compound 3 with 30% ellipsoid probability. Symmetry operation codes: i = −x, −y, −z; ii = −1 − x, −y, −z; iii = 1 − x, −y, −z.

structure, there are two metal centers, Cd1 and Cd2, and both are in the distorted pentagonal bipyramid geometry. The basal plane of Cd1 is formed by four chelating oxygen atoms (O3, O4, O12, and O13) from two fdc ligands and one nitrogen atom from the bridging bipyridyl ligand (N26). The apical positions are occupied by two water molecules (O1 and O2). On the other hand, the basal plane of the Cd2 centers is formed by four chelating oxygen atoms from the two fdc ligands (O15, O16, O24, and O25) and one water molecule (O14). The axial positions are occupied by the two nitrogen atoms (N37 and N40) from the two different bpe ligands; the ORTEP diagram with atom numbering scheme is shown in Figure 9. These Cd1 and Cd2 centers are bound with each other by the fdc and bpe ligands and form Cd12Cd22 motifs, which propagate along the crystallographic a-axis ultimately forming an S-type 1D strand. These 1D strands are in turn interpenetrated with each other forming a 1D + 1D → 3D framework (Figure 10). The interpenetrated 1D strands are held to each other by strong intramolecular O−H···O hydrogen bonds (Table S1, Supporting Information) (O(2)−H(2A)···O(3) [−x, −y + 1, −z − 1], O(2)−H(2B)···O(16) [−x, −y + 1, −z], O(14)−H(14A)··· O(7) [x − 1/2, −y + 3/2, z + 1/2], O(14)−H(14A)···O(13) [x − 1/2, −y + 3/2, z + 1/2], O(14)−H(14B)···O(4) [x − 1/ 2, −y + 3/2, z + 1/2], O(14)−H(14B)···O(7) [x − 1/2, −y + 3/2, z + 1/2]) with O···O distances between 2.767(5) and 2.969(5) Å. Again to understand the structure of 4 clearly, topological analysis by reducing multidimensional structure to a

square Cd4 motif, which is further linked via the fdc ligand in a double chelating fashion and propagates parallel to the crystallographic a-axis, ultimately forming a 1D tube-like channel along that direction. These 1D tubes are again interpenetrated with each other forming a 1D + 1D → 2D polycatenated MOF (Figure 7). The polycatenated 1D tubes are connected by intermolecular hydrogen bonding (O(1)− H(1B)···O(11) [−x, −y − 2, −z]) among the terminal water molecules and the carboxylate oxygen with H···O and O···O distances of 1.89(2) and 2.712(3) Å, respectively. The ethanol molecules are also entrapped within the channel by strong intermolecular hydrogen bonding (O(1)−H(1A)···O(100) [x, y − 1, z − 1] and O(100)−H(10)···O(2) [−x + 1, −y − 1, −z + 1]) with H···O and O···O distances of 1.94(4), 1.84(3), and 2.741(3) and 2.743 (3) Å (Table S1, Supporting Information), respectively. To further understand the structure of 3, topological analysis by reducing multidimensional structure to a simple node and linker net was performed. The topological analysis by TOPOS20 revealed that the structure is 4-c uninodal net with point symbol 45.6 having vertex symbol [4.4.4.4.4.*]. The simplified form of topological polycatenation among the 1D porous tubes in the compound 3 is displayed in Figure 8. Structure Description of [Cd(fdc)(1,2-bpe)(H2O)]n (4). Compound 4 crystallized in the space group P21/n with Z = 4 and is also a 1D + 1D → 3D polycatenated framework. In the

Figure 7. (a) Supramolecular structure of compound 3 and (b) 1D + 1D → 2D polycatenation present in compound 3. F



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Figure 9. ORTEP diagram of compound 4 with 30% ellipsoid probability. Symmetry operation codes: i = 1 − x, 2 − y, 1 − z; ii = −1 + x, y, z.

Figure 10. (a) 1D + 1D → 3D polycatenated 3D structure of compound 4 and (b) the 1D polymers that are penetrated with each other.

three chelating oxygen atoms of two fdc ligand (O12, O13, and O24) and one carboxylate oxygen atom (O4). The apical positions are occupied by one chelating oxygen atom (O23) and one carboxylate oxygen atom (O14); the ORTEP diagram with atom numbering scheme is shown in Figure 12. The Cd2 centers are bridged to the Cd1 centers in syn−anti fashion by the fdc ligands, and the Cd2 centers are also connected with each other in a double chelating fashion by the carboxylate

simple node and linker net was performed. The topological analysis by TOPOS20 revealed that the structure possesses a new binodal 3,4-c net with the point symbol {42.6}{44.62} (Figure 11, see Supporting Information for detailed calculation).19d−f

Figure 11. Simplified topological view of compound 4 showing 1D + 1D → 3D polycatenation.

Structure Description of [{Cd2(fdc)2(H2O)4}·(1,2-bpe)]n (5). Compound 5 crystallized in the space group P1̅ with Z = 1 and is a 2D layered framework with encapsulating the 1,2-bpe ligands within the layers. In the asymmetric unit, there are two types of metal centers, Cd1 and Cd2; both are in the distorted octahedral geometry. Cd2 centers are more distorted than the Cd1 centers. The basal planes of Cd1 centers are formed by four water molecules (O1, O1*, O2, and O2*, * = 1 − x, 2 − y, 1 − z). The axial positions are filled with two carboxylate oxygen atoms (O3 and O3*, * = 1 − x, 2 − y, 1 − z). On the other hand, the basal planes of Cd2 centers are formed by the

Figure 12. ORTEP diagram of compound 5 with 30% ellipsoid probability. Symmetry operation codes: i = 1 − x, 2 − y, 1 − z; ii = 2 − x, 2 − y, 1 − z; iii = 1 − x, 1 − y, 1 − z. G



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Figure 13. Three-dimensional supramolecular structure of compound 5 encapsulating the 1,2-bpe ligand (left) and 2D sheet structure present in the compound 5 (right).

Compounds 4 and 5 are stable up to 200 °C; after losing the water molecules, they continuously lose weight, and decomposition completes at around 400 °C (Figure 15).

ligand, forming a 2D dimensional network parallel to the crystallographic ab-plane (Figure 13). In the structure, the 1,2bpe ligands are not connected to the metal centers and are entrapped within the 2D layers by strong hydrogen bonds (O(1)−H(1B)···N(36) [−x + 1, −y + 1, −z + 1]) with H···N and O···N distances of 2.05(2) and 2.728(2) Å, respectively, and π····π stacking with the average distance 3.9 Å. Furthermore, the two water molecules O1 and O2 connected to the Cd1 center established four O−H···O hydrogen bonds with the fdc oxygens with O···O distances ranging from 2.728(2) to 2.914(2) Å (Table S1, Supporting Information). Here also, topological analysis by reducing multidimensional structure to a simple node and linker net was done, and the study revealed that this structure also possesses a new topology having binodal 4,6-c net with point symbol {32.42.52}{32.45.56.62}2 (Figure 14).19d−f

Figure 15. TG profiles of compounds 1−5.

Luminescent Properties. There exists a continuous interest in discovering framework compounds with d10 metal ions and organic chromophores, which have potential application in the field of photoactive materials for sensing (chemical sensors) and photochemistry.19,21 With the control over synthesis, it is now possible to tune the photoluminescence properties of the desired frameworks.21,22 In this regard, Cd(II) complexes having d10 electronic configuration demand much attention for their application potential in luminescence properties. Hence, the preparation of Cd(II) complexes can be an efficient method for developing new types of luminescent materials. In the present report, the roomtemperature photoluminescence properties have been investigated for compounds 1−5 in solid state (Figure 16) and compared with the respective free ligand. The emission spectrum of compound 1 shows a band peaking at 410 nm, which is the same as that of the fdc ligand (Figure S7, Supporting Information). For compounds 2 and 3, the emission spectrum deviates to the red relative to that of the fdc ligands, peaking at 432 nm. The emission spectra of compound 4 depend on the excitation wavelengths. For excitation wavelengths between 300 and 400 nm, the emission spectrum shows a peak around 420 nm resembling the free fdc ligand emission (Figure S7, Supporting Information), whereas at longer excitation wavelengths (400−450 nm), the emission spectrum deviates to the red, peaking around 540 nm. This

Figure 14. Simplified topological view of compound 5.

Thermal Stability (TGA) Studies. Thermal stability of all the compounds was checked in the temperature range RT to 800 °C. All compounds except compound 3 are stable up to 150−200 °C. Compound 1 is well stable up to 180 °C; then after losing the coordinated water molecules (weight loss 4.11%, calcd 4.08%), it starts losing weight sharply and decomposition completes at 380 °C. Compound 2 starts losing water at 155 °C; after losing four water molecules in the first step (weight loss 11.05%, calcd 10.85%), it loses another water molecule at around 195 °C (weight loss 2.61%, calcd. 2.71%), and then it continiously loses weight and completely decomposes at 630 °C. The decay of compound 3 is slightly complicated. It loses crystalline ethanol molecules first (weight loss 5.01%, calcd 4.95%), then rapidly loses the water and organic bridging ligand at 350 °C, and all the organic moieties decompose at 650 °C, leaving the oxide as the product. H



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{32.42.52}{32.45.56.62}2. The luminescence study reveals a dependence of the emission spectra on the MOF structures and proved the MOFs to be good luminescent materials with tunable emission in the visible spectral range.

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ASSOCIATED CONTENT

S Supporting Information *

Hydrogen bonding table, TOPOS calculations, PXRD, and more crystallographic information in cif format (CCDC 943517−943521). This material is available free of charge via the Internet at http://pubs.acs.org.

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Figure 16. Emission spectra of compounds 1 (350 nm), 2 (315 nm), 3 (320 nm), 4 (330 nm, solid line, and 400 nm, open circles), and 5 (405 nm). The excitation wavelength is indicated in parentheses.

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Tel: 351 234370368. Fax: 351 234370084. Notes

latter component may result from the contribution of the 1,2bpe ligand, whose emission spectrum is formed of two components around 440 nm19,21−23 and 520 nm,24 tentatively assigned to intraligand n−π* and π−π* transitions. Despite the presence of the same ligands, the emission spectra of compound 5 are independent of the excitation wavelength, revealing essentially the high-wavelength component from the 1,2-bpe ligand. The energy blue-shift observed between the emission spectra of the free ligands and that of the compounds was tentatively attributed to the presence of different kinds of structural motifs.23 It has been suggested that the deviation of the free ligand emission to the red can be assigned to an enhancement of the p-conjugation due to the complexation of the ligands to metal ions.25 Moreover, it is worth mentioning that the different emission spectra of compounds 4 and 5 highlight the fact that the bonds established by the ligands and the metal center also impact the emission properties.

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS R.S. thanks FCT for postdoctoral grants (SFRH/BPD/71798/ 2010).This work was supported by FCT, POCI2010, PEst-C/ CTM/LA0011/2013, FSE, and FEDER.

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CONCLUSION In summary, a series of Cd−fdc based MOFs with varied bridging amine ligands has been synthesized and characterized by different physicochemical methods and single crystal X-ray diffraction. Compounds 1−5 show interesting topological divergence. With the blocking amine, the 1D chain like structure was obtained, while with flexible or rigid bridging ligands, 1D ladder, 1D + 1D → 2D polycatenated MOF, 1D + 1D → 3D interpenetrated MOF, or simple layered 2D sheet encapsulating the amine ligand were formed. It is quite interesting to conclude that when the rigid 4,4′-bpy was used as a bridging amine, we get a uniform 1D tube like morphology, which are polycatenated with each other, but by using a flexible amine, 1,2-bipyridylethene, two types of MOFs formed depending on the temperature. In one case, the interpenetrated 3D framework formed with the interpenetrating units in wavy S-like strands, while at higher temperature, the ligands are encapsulated within the network through π···π interaction. For small rigid spacer amines, like pyrazine, the network completely changed to a ladder type chain compound. This study presents a new aspect of engineering innovative interpenetrated or polycatenated frameworks by tuning the rigidity or flexibility of the bridging amines and also the temperature. Topological studies revealed that compound 3 possesses a 4-c uninodal net with point symbol 45.6 having vertex symbol [4.4.4.4.4.*]. On the other hand, compound 4 has a new binodal 3,4-c net with the point symbol {42.6}{44.62}, whereas compound 5 also reveals a new topological binodal 4,6-c net having point symbol I



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