Synthesis and Characterization of Metal Complexes with Mixed 4

Article pubs.acs.org/crystal

Synthesis and Characterization of Metal Complexes with Mixed 4-Imidazole-Containing Tripodal Ligand and Varied Dicarboxylic Acid Shui-Sheng Chen,†,‡ Zhi-Hao Chen,† Jian Fan,† Taka-aki Okamura,§ Zheng-Shuai Bai,† Mei-Fang Lv,† and Wei-Yin Sun*,† †

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, China ‡ School of Chemistry and Chemical Engineering, Fuyang Teachers College, Fuyang 236041, China § Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan S Supporting Information *

ABSTRACT: Six new metal−organic coordination polymers [Mn(H3L)(ox)]·H 2 O (1), [Zn 2 (H 2 L)(pbdc)(μ 2 -OH)]·2H 2 O (2), [Co(H 3 L)(obea)]·3H2O (3), [Ni(H3L)(pbea)] (4), [Co(H3L)(pbea)(H2O)2] (5), and [Co4(H2L)2(pbea)3] (6) were synthesized by reactions of the corresponding metal salt with rigid tripodal ligand 1,3,5-tri(1H-imidazol-4yl)benzene (H3L) and different dicarboxylic acid of oxalic acid (H2ox), 1,4benzenedicarboxylic acid (H2pbdc), 1,2-phenylenediacetic acid (H2obea), 1,4-phenylenediacetic acid (H2pbea), respectively. The results of X-ray crystallographic analysis indicate that 1 and 3 are two-dimensional (2D) networks with 63-hcb topology, while 2 is (4,5)-connected three-dimensional (3D) net with Point (Schläfli) symbol of (42·52·72)(42·53·74·8). Complex 4 is a binodal (3,4)-connected 2D network with V2O5type topology. Complexes 5 and 6 were obtained through controlling reaction temperature, 5 features a one-dimensional (1D) chain, whereas 6 is an unprecedented tetra-nodal (3,4)-connected 3D net with Point (Schläfli) symbol of (4·62·103)(4·62)(4·64·8)2 attributable to the rich coordination modes of the ligands. The results of magnetic measurements showed that there are antiferromagnetic interactions in 1. Complex 2 exhibits intense light blue emission in the solid state at room temperature, while 3 shows water vapor adsorption property.

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INTRODUCTION Metal−organic frameworks (MOFs) are novel crystalline materials consisting of metal ions or clusters interconnected by a variety of organic linkers and have attracted considerable attention because of their potential applications in gas storage/ separation, photoactive materials, ion exchange, catalysis, magnetism, and so on.1−5 Hence, the most important factor for assembling desired MOFs is the judicious choice of appropriate linkers, including the length and specific functional and coordinating groups of the linkers,6 although synthetic conditions also have a great influence on the structure of the resulting complexes.7 The 1-imidazol-containing tripodal ligand 1,3,5-tris (1-imidazolyl)benzene (tib) is an efficient and versatile organic building unit for construction of coordination architectures and has been widely used in our previous studies, and the results showed that it can react with varied metal salts leading to the formation of MOFs with interesting structures, topologies, and properties.8 On the other hand, the polycarboxylates are the most extensively studied organic ligands in the construction of MOFs due to their versatile coordination modes,9,10 and especially the mixed polycarboxylate and N-containing ligands with more tunable factors are good candidates for the construction of novel MOFs.11,12 Taking the super compatibility in the construction of MOFs with mixed ligands into account, we © 2012 American Chemical Society

have further focused our attention on reactions of tib, varied Zn(II) salts together with different benzenedicarboxylic acids as the auxiliary ligand, and a series of novel complexes have been obtained based on the mixed system.13 On the basis of the study on 1-imidazol-containing versatile organic ligand tib, we designed a new tripodal 4-imidazole-containing ligand 1,3,5tri(1H-imidazol-4-yl)benzene (H3L) as an extension of our previous work. Compared with the 1-imidazol-containing ligand tib, the 4-imidazol-containing ligand H3L can serve as an anionic ligand when the 4-imidazol groups are deprotonated to generate imidazolate anion which will exhibit more versatile coordination modes in the process of assembly of coordination frameworks.14 On the basis of the deprotonation of 4-imidazol group, we have constructed two porous supramolecular isomeric frameworks with unique sorption properties.15 Considering the mixed polycarboxylate and N-containing ligands possessing more tunable factors in the construction of novel MOFs, we carried out the reactions of the 4-imidazolcontaining ligand H3L together with different carboxylate ligands and metal salts. Herein, we report the synthesis, crystal Received: December 8, 2011 Revised: March 28, 2012 Published: March 29, 2012 2315

dx.doi.org/10.1021/cg2016275 | Cryst. Growth Des. 2012, 12, 2315−2326

Crystal Growth & Design

Article

Ni(NO3)2·6H2O (29.1 mg, 0.1 mmol), NaOH (8.0 mg, 0.2 mmol), and 10 mL of H2O in a Teflon lined stainless steel container was performed at 160 °C for 3 days. Block crystals of 4 were isolated by filtration and washed by water and ethanol several times in 72% yield. Anal. Calcd for C25H20N6O4Ni: C, 56.96; H, 3.82; N, 15.94%. Found: C, 57.15; H, 3.89; N, 15.78%. IR (KBr pellet, cm−1): 3416(m, br), 3097(m, br), 2852(m), 1578 (s), 1414 (s), 1380 (s), 1126 (s), 1093 (m), 956 (m), 835 (s), 813(m), 755(m), 658 (s), 636 (w). Preparation of [Co(H3L)(pbea)(H2O)2] (5). Complex 5 was synthesized by the same procedure as that used for preparation of 4, except that Co(NO3)2·6H2O (29.1 mg, 0.1 mmol) was used instead of Ni(NO3)2·6H2O. Purple block crystals of 5 were obtained in 58% yield. Anal. Calcd for C25H24N6O6Co (%): C, 53.29; H, 4.29; N, 14.92%; Found: C, 53.48; H, 4.41; N, 14.82%. IR (KBr pellet, cm−1): 3419 (w), 3144(w), 2866(w), 1575 (s), 1415 (w), 1383(s), 1127 (w), 1095 (w), 993 (w), 835 (w), 755 (w), 688 (w), 654 (w), 628 (w). Preparation of [Co4(H2L)2(pbea)3] (6). Complex 6 was obtained by the same hydrothermal procedure as that for preparation of 5 except that the reaction mixture was heated at 210 °C. After the reaction mixture was cooled down to room temperature, purple black block crystals of 6 were collected with a yield of 42%. Anal. Calcd for C30H23N6O6Co2: C, 52.88; H, 3.40; N, 12.33%. Found: C, 52.57; H, 3.55; N, 12.19%. IR (KBr pellet, cm−1): 3426 (m, br), 3114(w), 1587 (s), 1524 (m), 1468 (w), 1431 (m), 1395 (w), 1292 (w), 1211(w), 1091 (w), 828 (w), 738 (w), 655 (w), 636 (w). Crystallography. The data collections for 1−3, 5, and 6 were carried out on a Bruker Smart Apex CCD area-detector diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 20(2) °C. The diffraction data were integrated by using the SAINT program.17 Semiempirical absorption corrections were applied using the SADABS program.18 The crystallographic data for 4 were collected on a Rigaku RAXIS-RAPID II imaging plate area detector with Mo−Kα radiation (0.71075 Å) using MicroMax-007HF microfocus rotating anode X-ray generator and VariMax-Mo optics at −173 °C. The structures of 1−6 were solved by direct methods, and all nonhydrogen atoms were refined anisotropically on F2 by the full-matrix least-squares technique using the SHELXL-97 crystallographic software package.19 The hydrogen atoms of the ligands were generated geometrically. The details of the crystal parameters, data collection, and refinements for the complexes are summarized in Table 1, and selected bond lengths and angles with their estimated standard deviations are listed in Table 2.

structure, and properties of six new coordination polymers [Mn(H3L)(ox)]·H2O (1), [Zn2(H2L)(pbdc)(μ2-OH)]·2H2O (2), [Co(H3L)(obea)]·3H2O (3), [Ni(H3L)(pbea)] (4), [Co(H3L)(pbea)(H2O)2] (5), and [Co4(H2L)2(pbea)3] (6) obtained by reactions of H3L and different carboxylic acids of oxalic acid (H2ox), 1,4-benzenedicarboxylic acid (H2pbdc), 1,2-phenylenediacetic acid (H2obea), and 1,4-phenylenediacetic acid (H2pbea) with corresponding metal salts under hydrothermal conditions.

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EXPERIMENTAL SECTION

All commercially available chemicals are of reagent grade and were used as received without further purification. The ligand H3L was prepared according to the literature.15,16 Elemental analyses of C, H, and N were taken on a Perkin-Elmer 240C elemental analyzer at the analysis center of Nanjing University. Infrared spectra (IR) were recorded on a Bruker Vector22 FT-IR spectrophotometer by using KBr pellets. Thermogravimetric analyses (TGA) were performed on a simultaneous SDT 2960 thermal analyzer under nitrogen with a heating rate of 10 °C min−1. The luminescence spectra for the powdered solid samples were measured on an Aminco Bowman Series 2 spectrofluorometer with a xenon arc lamp as the light source. In the measurements of emission and excitation spectra the pass width is 5 nm, and all the measurements were carried out under the same experimental conditions. Powder X-ray diffraction (PXRD) patterns were measured on a Shimadzu XRD-6000 X-ray diffractometer with Cu Kα (λ = 1.5418 Å) radiation at room temperature. Solid state UV− visible spectra were obtained in diffuse reflectance mode on a Shimadzu UV3600 spectrophotometer coupled to a MPC-3100 unit equipped with an integrating sphere coated with BaSO4. The magnetic measurements in the temperature range of 1.8−300 K were carried out on a Quantum Design MPMS7 SQUID magnetometer in a field of 2000 Oe. Diamagnetic corrections were made with Pascal’s constants. The sorption experiments were performed on a Belsorp-max volumetric gas sorption instrument. The sample was activated by using the “outgas” function of the surface area analyzer for 24 h at 180 °C. Preparation of [Mn(H3L)(ox)]·H2O (1). A reaction mixture of H3L (27.6 mg, 0.1 mmol), MnCl2·4H2O (20.0 mg, 0.1 mmol), H2ox·2H2O (12.6 mg, 0.1 mmol), and NaOH (8.0 mg, 0.2 mmol) in 10 mL of H2O was sealed in a 16 mL Teflon lined stainless steel container and heated at 180 °C for 3 days. After being cooled to room temperature, purple block crystals of 1 were collected by filtration and washed by water and ethanol several times with a yield of 65%. Anal. Calcd for C17H14N6O5Mn (%): C, 46.69; H, 3.23; N, 19.22%; Found: C, 46.42; H, 3.45; N, 19.35%. IR (KBr pellet, cm−1): 3245−3136(m), 2848−2636(m), 1677(s), 1615(s), 1487(m), 1315(s), 1126(s), 1095(m), 865(m), 817(m), 791(m), 756(s), 643(m), 515(w). Preparation of [Zn2(H2L)(pbdc)(μ2-OH)]·2H2O (2). A mixture of H3L (27.6 mg, 0.1 mmol), ZnSO4·7H2O (57.6 mg, 0.2 mmol), H2pbdc (33.2 mg, 0.2 mmol), and NaOH (16.0 mg, 0.4 mmol) in 10 mL of H2O was sealed in a 16 mL Teflon lined stainless steel container and heated at 170 °C for 3 days. After the reaction mixture was cooled to room temperature, colorless block crystals of 2 were collected by filtration and washed with water and ethanol several times with a yield of 42%. Anal. Calcd for C23H20N6O7Zn2: C, 44.33; H, 3.23; N, 13.48%. Found: C, 44.32; H, 3.49; N, 13.57%. IR (KBr pellet, cm−1): 3412 (m, br), 3142 (m, br), 1618 (w), 1571 (s), 1502 (w), 1480 (w), 1381 (s), 1314 (w), 1136 (m), 1102 (w), 966 (w), 873 (w), 843 (m), 744 (m), 642(m), 563 (w), 523 (w). Preparation of [Co(H3L)(obea)]·3H2O (3). Reaction of H3L (27.6 mg, 0.1 mmol), Co(NO3)2·6H2O (29.1 mg, 0.1 mmol), H2obea (19.4 mg, 0.1 mmol), NaOH (8.0 mg, 0.2 mmol) and 10 mL of H2O in a 16 mL Teflon lined stainless steel container at 160 °C for 3 days produced purple block crystals of 3 in 66% yield. Anal. Calcd for C25H26N6O7Co: C, 51.64; H, 4.51; N, 14.45%. Found: C, 51.84; H, 4.37; N, 14.30%. IR (KBr pellet, cm−1): 3421 (m, br), 1579 (s), 1456 (w), 1384 (s), 1272 (w), 1127 (m), 1096(m), 995 (w), 830 (w), 714 (w), 648 (w), 627 (w), 576 (w). Preparation of [Ni(H3L)(pbea)] (4). Hydrothermal treatment of H3 L (27.6 mg, 0.1 mmol), H 2pbea (19.4 mg, 0.1 mmol),

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RESULTS AND DISCUSSION Description of Crystal Structures. Complex [Mn(H3L)(ox)]·H2O (1). The result of X-ray diffraction analysis revealed that complex 1 crystallizes in triclinic form with space group of P1̅ and the asymmetric unit consists of one Mn(II) atom, one H3L, two halves of ox2−, and one free water molecule. As shown in Figure 1a, each Mn(II) atom is six-coordinated by two N (N5, N2A) atoms of two different H3L ligands and two pairs of O (O1, O2B and O3, O4C) atoms of chelating carboxylate groups from two different ox2− (Type I, Scheme 1) forming octahedral coordination geometry. The Mn−O bond distances range from 2.170(2) to 2.265(2) Å, while the Mn−N ones are 2.195(2) and 2.207(2) Å, respectively, and the coordination angles around the Mn1 are in the range of 73.15(7)−160.44(9)° (Table 2). Each oxalate anion acts as a bridging ligand to link two Mn(II) atoms to form a zigzag one-dimensional (1D) chain with Mn···Mn distance of 5.67 Å and Mn···Mn···Mn angle of 119.682(9)° running along the a axis (Figure 1b). Furthermore, in complex 1, the zigzag Mn(ox) chains are further connected by H3L ligands to form a two-dimensional (2D) network, in which two of three imidazolyl groups of H3L coordinate with Mn(II) atom, while the third one is free of coordination as shown in Figure 1c. Topologically, the adjacent Mn(II) atoms act as three-connected nodes to link each other by 2316



Article

Crystal Structure of [Zn2(H2L)(pbdc)(μ2-OH)]·2H2O (2). Structural analysis revealed that the asymmetric unit of 2 consists of two Zn(II) atoms, one H2L−, one pbdc2−, one μ2hydroxo bridge (μ2-OH), and two free water molecules. Two crystallographically independent Zn(II) atoms are connected by a hydroxo bridge with a Zn···Zn distance of 3.395 Å, and Zn1 is four-coordinated by two N atoms from two different H2L− ligands and two O atoms from one pbdc2− and one μ2OH to form a distorted tetrahedral coordination geometry, while Zn2 with a N2O3 donor set adopts a distorted squarepyramidal coordination geometry by the coordination of two carboxylate O atoms from one pbdc2− ligand, one O from μ2OH, and two N atoms from two H2L− ligands as shown in Figure 2a. The Zn−O bond lengths are in the range of 1.946(4)−2.261(5) Å and Zn−N ones vary from 1.972(5)− 2.024(5) Å (Table 2). On the other hand, each pbdc2− acts as a linear ligand to link two Zn(II) atoms using its two carboxylate groups with μ1-η1:η0-monodentate and μ1-η1:η1-chelating modes, respectively (Type II, Scheme 1). It should be noticed that one of the three 4-imidazole groups of H3L is deprotonated to give H2L− in 2. The deprotonated imidazolate anions together with the μ2-OH bridges link Zn(II) atoms to form an infinite 1D chain (Figure 2b), and two imidazole groups of each H2L− coordinate with Zn(II) atoms to form a 2D network (Figure 2c), which is further connected by the third imidazole group of H2L− to give a 3D framework via Zn−N coordination interactions (Figure 2d). Interestingly, the linear pbdc2− ligands also act as “pillars” to link Zn(II) atoms of the adjacent 2D layers similar to the third imidazole groups (Figure 2d). Much effort has been devoted to the study of framework connectivity and topological analysis, which has been demonstrated to be a useful and simple method to analyze the extended frameworks, especially for the complicated 3D frameworks.21 Since the Zn1 and Zn2 atoms are bridged by the μ2-hydroxo group (vide supra), it can be considered as a binuclear [Zn2(OH)] subunit. In this sense, each [Zn2(OH)] binuclear unit in 2 is surrounded by four H2L− and another [Zn2(OH)] subunit by virtue of the pillared pbdc2− ligand to afford a five-connecting node, while each H2L− linking four [Zn2(OH)] subunits can be defined as four-connector. Therefore, the resulting structure of 2 is an extended binodal (4, 5)-connected 3D net with Point (Schläfli) symbol of (42·52·72)(42·53·74·8) (Figure 2e). Crystal Structure of [Co(H3L)(obea)]·3H2O (3). When Co(NO3)2·6H2O and H3L were used to react with flexible H2obea ligand, complex 3 with a different structure was obtained. Figure 3a shows the coordination environment of the Co(II) atom with the atom numbering scheme. Co1 atom is in a distorted tetrahedral coordination environment with three N atoms from three distinct H3L ligands with Co−N bond distances of 2.017(3), 2.022(3), and 2.036(3) Å and one O atom from a ligand obea2− with a Co−O bond distance of 1.985(3) Å and the bond angles around Co1 in the range of 101.61(13)−124.29(13)° (Table 2). It is noteworthy that the flexible cis-obea2− ligand acts as a terminal ligand to coordinate with the Co(II) atom with one carboxylate group in μ1-η1:η0-monodentate coordination mode and another carboxylic group deprotonates to balance the charge of the complex but is free of coordination (Type III, Scheme 1). In complex 3, Co(II) atoms serve as trigonal nodes, and each H3L ligand in turn connects three Co(II) atoms to form a triangle with edge lengths (Co···Co) of 10.92, 11.82, and 12.66 Å, respectively (Figure 3b). Therefore, the formation of network with (6, 3) topology is

Table 1. Crystal Data and Refinement Results for Complexes 1−6 compound

1

2

3

empirical formula formula weight temperature/K crystal system space group a (Å) b (Å) c (Å) a (°) β (°) γ (°) V (Å3) Z Dc (g cm−3) F(000) θ range /° reflections collected independent reflections goodness-of-fit on F2 R1 [I > 2σ(I)]a wR2 [I > 2σ(I)]b compound

C17H14N6O5Mn

C23H20N6O7Zn2

C25H26N6O7Co

437.27 293(2) triclinic P1̅ 7.6017(16) 9.873(2) 12.050(3) 91.991(4) 93.712(4) 96.626(4) 895.6(3) 2 1.614 442 1.70−25.49 4646

623.15 293(2) monoclinic P21/n 11.841(4) 15.942(6) 13.104(4) 90 102.542(7) 90 2414.5(14) 4 1.700 1244 2.04−26.01 12857

581.40 293(2) monoclinic P2/c 13.4051(13) 11.8197(12) 20.1860(15) 90 127.807(4) 90 2527.0(4) 4 1.512 1180 2.05−25.24 12553

3265

4742

4571

1.073

1.029

1.010

0.0460 0.1264

0.0615 0.1479

0.0605 0.1179

empirical formula formula weight temperature/K crystal system space group a (Å) b (Å) c (Å) a (°) β (°) γ (°) V (Å3) Z Dc (g cm−3) F(000) θ range /° reflections collected independent reflections goodness-of-fit on F2 R1 [I > 2σ(I)]a wR2 [I > 2σ(I)]b

4

5

6

C25H20N6O4Ni 527.18 200 monoclinic P21/c 13.400(2) 12.5628(17) 14.279(3) 90 107.719(7) 90 2289.6(7) 4 1.529 1088 3.00−27.48 21825

C25H24N6O6Co 563.40 293(2) triclinic P1̅ 8.6962(10) 9.3262(11) 15.8629(19) 74.271(2) 75.232(2) 80.071(2) 1190.0(2) 2 1.561 574 2.28−25.10 5980

C30H23N6O6Co2 681.40 293(2) orthorhombic Pbca 8.4623(9) 21.721(2) 29.534(3) 90 90 90 5428.7(10) 8 1.667 2776 1.88−25.25 25911

5252

4153

4891

1.080

1.126

1.023

0.0346 0.0816

0.0430 0.1256

0.0388 0.0947

R1 = Σ||Fo| − |Fc||/Σ|Fo|. bwR2 = |Σw(|Fo|2 − |Fc|2)|/Σ|w(Fo)2|1/2, where w = 1/[σ2(Fo2) + (aP)2 + bP]. P = (Fo2 + 2Fc2)/3 a

the linear ligands into a 63-hcb net (Figure 1d).20 The 2D layers are further linked together by N−H···O and C−H···O hydrogen bonds to produce a three-dimensional (3D) framework (Figure 1e). The hydrogen bonding data are summarized in Table S1, Supporting Information. The free water molecules locate in the voids formed between two adjacent layers and are held there by C−H···O hydrogen bonds. 2317



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Table 2. Selected Bond Distances (Å) and Angles (deg) for Complexes 1−6a 1 Mn(1)−O(1) Mn(1)−O(4)#2 Mn(1)−N(5) O(4)#2−Mn(1)−N (2)#3 N(2)#3−Mn(1)−O (3) N(2)#3−Mn(1)−N (5) O(4)#2−Mn(1)−O (2)#1 O(3)−Mn(1)−O(2) #1 O(4)#2−Mn(1)−O (1) O(3)−Mn(1)−O(1) 2 Zn(1)−O(5) Zn(1)−O(1) Zn(2)−O(5) Zn(2)−N(3)#3 Zn(2)−O(3)#4 O(5)−Zn(1)−N(1) #1 N(1)#1−Zn(1)−O (1) N(1)#1−Zn(1)−N (5) O(5)−Zn(2)−N(2) #2 N(2)#2−Zn(2)−N (3)#3 N(2)#2−Zn(2)−O (4)#4 O(5)−Zn(2)−O(3) #4 N(3)#3−Zn(2)−O (3)#4 3 Co(1)−O(2) Co(1)−N(4)#1 O(2)−Co(1)−N(6) N(6)−Co(1)−N(4) #1 N(6)−Co(1)−N(1) #2

2.265(2) 2.170(2) 2.207(2) 115.45(9) 87.59(9) 104.95(10) 159.96(8) 108.31(8) 87.88(8) 85.14(8)

Mn(1)−O(2)#1 Mn(1)−N(2)#3

2.225(2) 2.195(2)

O(4)#2−Mn(1)−O (3) O(4)#2−Mn(1)−N (5) O(3)−Mn(1)−N(5)

75.61(7)

N(2)#3−Mn(1)−O (2)#1 N(5)−Mn(1)−O(2) #1 N(2)#3−Mn(1)−O (1) N(5)−Mn(1)−O(1)

84.54(8)

85.36(9)

88.10(9) 152.92(9) 89.74(9)

Zn(1)−N(1)#1 Zn(1)−N(5) Zn(2)−N(2)#2 Zn(2)−O(4)#4 O(5)−Zn(1)−O(1)

117.79(18)

117.31(19)

O(5)−Zn(1)−N(5)

96.56(18)

110.1(2)

O(1)−Zn(1)−N(5)

99.6(2)

107.12(17)

O(5)−Zn(2)−N(3) #3 O(5)−Zn(2)−O(4) #4 N(3)#3−Zn(2)−O (4)#4 N(2)#2−Zn(2)−O (3)#4 O(4)#4−Zn(2)−O (3)#4

94.71(19)

Co(1)−N(6) Co(1)−N(1)#2 O(2)−Co(1)−N(4) #1 O(2)−Co(1)−N(1) #2 N(4)#1−Co(1)−N (1)#2

2.017(3) 2.036(3) 124.29(13)

102.0(2) 91.17(17) 137.86(19)

1.985(3) 2.022(3) 111.22(13) 108.06(13) 105.55(13)

O(1)−Ni(1)−N (112) O(1)−Ni(1)−N (152)#3 O(2)−Ni(1)−N (112) O(2)−Ni(1)−N (152)#3 O(3)#1−Ni(1)−N (132)#2 N(112)−Ni(1)−N (132)#2 5 Co(1)−O(1W) Co(1)−O(2W) Co(1)−O(3) O(1W)−Co(1)−N (1) N(1)−Co(1)−O (2W) N(1)−Co(1)−N(5) #1 O(1W)−Co(1)−O (3) O(2W)−Co(1)−O (3) 6 Co(1)−N(1) Co(1)−O(4)#1 Co(2)−O(1)#3 Co(2)−N(2) N(1)−Co(1)−O(3)

160.44(9)

1.946(4) 1.981(4) 1.964(4) 2.024(5) 2.261(5) 112.09(19)

110.7(2)

4 Ni(1)−O(1) Ni(1)−O(3)#1 Ni(1)−N(132)#2 O(1)−Ni(1)−O(2)

1.972(5) 2.016(5) 1.998(5) 2.177(5)

143.66(19) 94.90(19) 107.23(19) 59.26(18)

O(3)−Co(1)−O(4) #1 O(3)−Co(1)−N(4) #2 O(1)#3−Co(2)−O (5) O(5)−Co(2)−N(2)

104.07(12)

2.1162(12) 2.0623(12) 2.0878(17) 60.76(4) 96.93(5) 86.47(5) 157.48(5) 87.84(4) 100.45(5) 91.80(5)

2.013(2) 2.037(2) 2.117(2) 135.02(10) 118.67(9) 100.86(9) 82.88(9)

2.2185(11) 2.0575(13) 2.0748(14) 163.11(4) 85.57(5) 103.91(4) 83.85(5) 98.61(5) 85.86(5) 94.18(5)

Co(1)−N(1) Co(1)−N(5)#1

2.033(2) 2.081(2)

O(1W)−Co(1)−O (2W) O(1W)−Co(1)−N (5)#1 O(2W)-Co(1)−N(5) #1 N(1)−Co(1)−O(3)

103.64(9) 92.49(9) 91.01(9) 83.23(9)

89.09(10)

N(5)#1−Co(1)−O (3)

175.26(8)

1.971(2) 1.987(2) 1.9647(19) 2.007(2) 127.53(9)

Co(1)−O(3) Co(1)−N(4)#2 Co(2)−O(5) Co(2)−N(5)#4 N(1)−Co(1)−O(4) #1 N(1)−Co(1)−N(4) #2 O(4)#1−Co(1)−N (4)#2 O(1)#3−Co(2)−N (2) O(1)#3−Co(2)−N (5)#4 N(2)−Co(2)−N(5) #4

1.983(2) 2.026(2) 2.003(2) 2.025(2) 108.23(10)

103.10(8) 95.75(9) 103.64(9) 118.71(9)

101.61(13) O(5)−Co(2)−N(5) #4

Ni(1)−O(2) Ni(1)−N(112) Ni(1)−N(152)#3 O(1)−Ni(1)−O(3) #1 O(1)−Ni(1)−N (132)#2 O(2)−Ni(1)−O(3) #1 O(2)−Ni(1)−N (132)#2 O(3)#1−Ni(1)−N (112) O(3)#1−Ni(1)−N (152)#3 N(112)−Ni(1)−N (152)#3

93.92(9)

117.31(10) 101.32(9) 113.58(9) 118.11(9) 107.83(9)

Symmetry transformations used to generate equivalent atoms: For 1: #1 −x + 1, −y + 1, −z + 1, #2 −x + 1, −y, −z + 1, #3 −x + 1, −y + 1, −z. For 2: #1 −x + 1/2, y + 1/2, −z + 3/2, #2 −x + 1, −y + 1, −z + 2, #3 x + 1/2, −y + 3/2, z − 1/2, #4 −x + 2, −y + 1, −z + 1. For 3: #1 x, y + 1, z, #2 x, −y + 1, z − 1/2. For 4: #1 −x + 1, −y, −z + 1, #2 −x, −y + 1, −z + 1, #3 −x + 1, −y + 1, −z + 1. For 5: #1 x − 1, y + 1, z. For 6: #1 x − 1/2, y, −z + 1/2, #2 −x + 1, y + 1/2, −z + 1/2, #3 −x + 1, y − 1/2, −z + 1/2, #4 x + 1/2, y, −z + 1/2. a

enhanced by using tripodal ligand H3L enclosing an angle about 120°. In each 2D layer of complex 3, the plane formed by Co(II) atoms and central benzene ring planes of H3L ligands are coplanar, while the imidazole ring planes deviate from the benzene ring planes with dihedral angles of 18.65°, 32.30°, and 37.68° in each H3L ligand. Such a coordination mode makes the compound a 2D network with a honeycomb structure with typical 63-hcb topology (Figure 3c). It can be seen clearly that the 2D layers repeat in an ···ABAB··· stacking sequence along the b axis, and N−H···O, C−H···O hydrogen bonds of adjacent layers further consolidate the 2D framework (Figure 3d). Particularly, two imidazole rings

of the H3L ligands between the adjacent 2D layers are nearly parallel with a dihedral angle of 2.37° and are separated by a centroid−centroid distance of 3.59 Å, indicating the presence of π−π stacking interactions.22 Such π−π interactions link the 2D layers to a 3D framework (Figure 3e) with 1D channels occupied by water molecules (Figure 3f). PLATON analysis shows that the structure of 3 consists of voids of 415.8 Å3 that represent 16.5% per unit cell volume of 2527.0 Å3 upon removal of the guest water molecules. Crystal Structure of [Ni(H3L)(pbea)] (4). Compound 4 crystallizes in the monoclinic space group P21/c. As shown in Figure 4a, the fundamental unit of 4 contains one Ni(II) center 2318



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Scheme 1. Coordination Modes of ox2−, pbdc2−, obea2−, and pbea2− Ligands Appeared in 1−6

ligands link four Ni(II) atoms to form a metallocycle with intermetallic distances of Ni1A···Ni1B = Ni1C···Ni1D = 7.35 Å and Ni1A···Ni1D = Ni1B···Ni1C = 13.40 Å. Accordingly, each A ring is surrounded by two other A rings and two B rings, while each B ring neighbors upon four A rings and two B rings (Figure 4c). From the view of topology, if the Ni(II) atom is considered as a 4-connected node, H3L is viewed as a 3connector, and the bridging pbea2− ligand is regarded as a linear linker. Therefore, the structure of 4 can be defined as a binodal (3, 4)-connected V2O5-type network with (42·63·8)(42·6) topology (Figure 4d).23 Furthermore, the 3D structure is generated and consolidated by the packed 2D layers joined by N−H···O and C−H···O hydrogen bonds (Figure 4e, Table S1, Supporting Information). Crystal Structure of [Co(H3L)(pbea)(H2O)2] (5). When Co(NO3)2·6H2O, instead of Ni(NO3)2·6H2O, was used in the reaction, 5 with a different structure was isolated. Compound 5 crystallizes in the triclinic space group P1̅. As shown in Figure 5a, the central Co(II) atom is five-coordinated by two N atoms from two different H3L ligands and three O atoms from one pbea2− ligand and two coordinated water molecules to form distorted square-pyramidal coordination geometry. The Co−O and Co−N bond lengths and coordination angles around Co(II) are in the normal range as listed in Table 2. Each H3L uses its two of three imidazol groups to link Ni(II) atoms to form an infinite 1D chain, while the third imidazole group of H3L is free of coordination. The cis-pbea2− uses one carboxylate

Figure 1. (a) The coordination environment of Mn(II) atom in 1 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms and water molecule are omitted for clarity. Symmetry code: A 1 − x, 1 − y, −z, B 1 − x, 1 − y, 1 − z, C 1 − x, −y, 1 − z. (b) The 1D chain of Mn(II)-ox2−. (c) The 2D (6, 3) network structure of 1. (d) The representation of 63-hcb framework. (e) 3D framework of 1 linked by hydrogen bonds indicated by a dashed line.

which adopts a distorted octahedral geometry with N3O3 donor set and is coordinated by three N atoms from three different H3L ligands and three carboxylate O ones from two different pbea2−. On the other hand, each H3L ligand in turn links three Ni(II) atoms to generate an infinite 1D chain structure (Figure 4b) rather than the 2D (6, 3) network based on Co(II)-H3L in 3, and each pbea2− ligand acts as a μ2-bridge using its two carboxylate groups in μ1-η1:η0-monodentate and μ1-η1:η1chelating modes (Type IV, Scheme 1) to link two Ni(II) atoms of adjacent 1D chains to generate a 2D network with different metallocycles A and B (Figure 4c). In A, two H3L ligands connect two Ni(II) atoms to form a 20-membered ring with a Ni···Ni (e.g., Ni1D···Ni1E in Figure 4c) distance of 11.26 Å. In B, two H3L ligands together with four pbea2− 2319



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and dimensionality of the frameworks by thermal desolvation and changing the coordination modes.24 When the reaction temperature was changed to 210 °C in the preparation reaction, a new complex 6 with a different structure was isolated. Complex 6 crystallizes in orthorhombic space group Pbca, rather than the triclinic space group P1̅ that appeared in 5 (Table 1). There are two Co(II) atoms, one deprotonated H2L−, one and half of pbea2− ligands in the asymmetric unit of 6 as shown in Figure 6a. The Co1 atom is four-coordinated by two N atoms (N1, N4A) from two different H2L− and two O ones (O3, O4B) from two different pbea2− ligands. The average Co1−O and Co1−N distances are 1.985(2) and 1.999(2) Å, respectively, and the coordination angles around Co1 varies from 95.75(9) to 127.53(9)° (Table 2). Co2 is coordinated by two O atoms (O5, O1D) from two different pbea2− ligands, and two N ones (N2, N5C) from two H2L− to complete a distorted tetrahedral coordination environment with normal bond lengths and angles as listed in Table 2. In 6, there are two kinds of pbea2− with different conformations and coordination modes of the carboxylate groups: μ1-η1:η0-monodentate, μ2η1:η1-bis-monodentate (Types VI and VII, Scheme 1). It should be noticed that one 4-imidazol group of H3L has been deprotonated to give an imidazolate anion to coordinate with two Co(II) atoms, and thus the overall H2L− employs as a μ4bridge to link four Co(II) atoms. The dihedral angles between each imidazole group and central benzene ring plane are 34.83°, 37.30°, and 56.15°, respectively, which are highly distorted in order to meet the coordination requirement by the conformational variance of aryl plane. Therefore, the ligands exhibit versatile coordination modes compared with that in complex 5. In 6, two different kinds of completely deprotonated pbea2− serve as two- or three-connectors to coordinate with two or three Co(II) atoms to generate a puckered 2D network if the coordination of H2L− with Co(II) is neglected (Figure 6b), while the deprotonated H2L− ligands act as fourconnected node to also link Co(II) atoms into 2D net without considering the coordination of pbea2− (Figure 6c). Furthermore, the two kinds of Co(II) atoms as four-connectors are in turn connected by H2L− and pbea2− to give rise to the complicated 3D framework (Figure 6d). Topologically, the overall framework of 6 was accordingly simplified as illustrated in Figure 6e, which is an unprecedented tetra-nodal (3, 4)connected net with its Point (Schläfli) symbol of (4·62·103)(4·62)(4·64·8)2. Synthesis of the Complexes and Comparison of the Structures. Six metal(II) coordination polymers were successfully synthesized and structurally characterized using rigid tripodal ligand H3L in the presence of varied carboxylate anions. The Zn(II) complex (2) is colorless while the Mn(II), Co(II), and Ni(II) ones show different colors as reflected by the solid state UV−visible spectra shown in Figure S1, Supporting Information. As mentioned above, the 4-imidazolcontaining ligand H3L can exhibit versatile coordination modes: in complexes 1, 3, 4, and 5, H3L acts as a two- or threeconnected neutral ligand to meet the different coordination requirements of the metal centers by virtue of the coordination of different amounts of imidazolyl groups and their varied conformations defined by dihedral angles between the imidazole ring plane and the central benzene ring plane, whereas, in 2 and 6, H3L has been partially deprotonated to generate a four-connected H2L− anion participating in the construction of MOFs. Similarly, the auxiliary carboxylate ligands play different roles in the construction of the complexes: ox2−

Figure 2. (a) The coordination environment of Zn(II) atoms in 2 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms and water molecule are omitted for clarity. Symmetry code: A 0.5 − x, 0.5 + y, 1.5 − z, B 1 − x, 1 − y, 2 − z, C 1 − x, −y, 1 − z, D 2 − x, 1 − y, 1 − z. (b) The 1D chain of Mn(II) bridged by imidazolate anion and OH−. (c) 2D network of 2 formed by two of three imidazole groups of H2L− coordinating with Zn(II) atoms. (d) 3D structure of 2 constructed from the 2D networks pillared by the third imidazole group (pink) and pbdc2− ligands (green). (e) Schematic representation of the binodal (4, 5)-connected 3D framework of 2 with (42·52·72)(42·53·74·8) topology.

group in μ1-η1:η0-monodentate mode to coordinate with Co(II) atom as a terminal ligand (Type V, Scheme 1). The 1D chains repeat in an ···ABAB··· stacking sequence and N−H···O, C−H···O hydrogen bonds of adjacent chains further link the 1D chains to a 2D network (Figure 5c). Crystal Structure of [Co4(H2L)2(pbea)3] (6). In 5, the overall structure is 1D chain due to the existence of uncoordination sites of H3L and pbea2− ligands. It has been reported that the reaction temperature is important in controlling the topology 2320



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Figure 3. (a) The coordination environment of Co(II) atom in 3 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms and water molecule are omitted for clarity. Symmetry code: A x, 1 − y, −0.5 + z, B x, 1 + y, z. (b) The 2D (6, 3) network structure of Co(II)-H3L. (c) The representation of 63-hcb framework. Turquoise balls: Co; pink balls: the centroid of H3L ligand. (d) The packing diagram of 2D layers linked by hydrogen bonds in 3. (e) The 3D framework packed by π−π stacking interactions of imidazolyl groups highlighted by the pink circle. (f) The 1D channels in 3 occupied by water molecules.

as bridge linking Mn(II) to give an infinite 1D chain in 1, pbdc2− in 2 and pbea2− in 4 as pillars linking adjacent metal(II) atoms, obea 2− in 3 and pbea 2− in 5 just as a terminal ligand and different pbea 2− in 6 as bridge linking Co(II) to form 2D layer. It is noteworthy that the flexible pbea 2− ligands in 4, 5, 6 exhibit varied coordination modes to meet the coordination requirements of metal centers (Types IV, V, VI, and VII, Scheme 1). The remarkable difference between the structures of 5 and 6 implies the great influence of the hydrothermal reaction temperature. Changing the reaction temperature from 160 to 210 °C leads to the dimensionality variation from 1D in 5 to 3D in 6. Complex 5 has more coordinated water molecules in the structure while in 6 the coordinated water molecules completely disappeared just by increasing the reaction temperature. A similar phenomenon

has been observed in the case of cobalt(II) succinate and other complexes.25 Thermal Stabilities and Powder X-ray Diffraction of the Complexes. Complexes 1−6 were subjected to thermogravimetric analysis (TGA) to ascertain the stability of their respective supramolecular architectures (Figure S2, Supporting Information). Complex 1 shows a weight loss of 4.17% around 180 °C corresponding to the release of free water molecules (calc. 4.12%), and the decomposition of the residue occurred at 360 °C. For 2, a weight loss of 5.81% was observed in the temperature range of 240−305 °C, which corresponds to the loss of the coordinated water molecules (calc. 5.78%), and further weight loss was observed at about 410 °C. For 3, a weight loss starts at 110 °C with the liberation of the free water molecules with a weight of 9.01% (calc. 9.29%), and the 2321



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Figure 4. (a) The coordination environment of the Ni(II) atom in 4 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A −x, 1 − y, 1 − z, B 1 − x, 1 − y, 1 − z, C 1 − x, −y, 1 − z. (b) The 1D chain of Ni(II)-H3L. (c) The 2D network with 22- and 44-membered metallacycles in 4. (d) Schematic representation of the V2O5 topology of 4. (e) 3D framework of 4 linked by hydrogen bonds indicated by a dashed line.

Figure 5. (a) The coordination environment of Co(II) atom in 5 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A −1 + x, 1 + y, z. (b) The 1D chain in 5. (c) The 2D network formed by the packing 1D chains linked by hydrogen bonds in 5.

decomposition of the residue observed at about 405 °C. A total weight loss of 6.49% was observed for 5 in the temperature range of 195−255 °C, which is attributed to the loss of the coordinated water molecules (calc. 6.39%), and the residue is stable up to about 470 °C. No obviously weight losses were found for complexes 4 and 6 before the decomposition of the framework occurred at about 220 and 380 °C respectively, which are in good agreement with the results of the crystal structural analysis. The pure phase of the complexes was proved by powder X-ray diffraction (PXRD), where the patterns of assynthesized 1−6 are consistent with the corresponding simulated ones (Supporting Information, Figure S3). Sorption Property. There are free or coordinated water molecules in the complexes, except 4 and 6 without solvent molecules, and 3D frameworks are formed by coordination and hydrogen bonding/π−π interactions as described above. Thus, the sorption property was investigated. After testing, it was found that the water molecules in 3 and 5 can be removed completely to give dehydrated samples of 3′ and 5′, respectively,

without destroying the structure (Figure S4, Supporting Information). As shown in Figure 7a, N2 sorption isotherm of the dehydrated solid 3′ suggests only surface adsorption which may be due to the large kinetic diameter (3.6 Å) of the N2 molecule; however, the H2O vapor sorption of 3′ was observed as illustrated in Figure 7b. The adsorption amount, 7.04 wt % of H2O at 298 K and 1 atm (87.64 cm3/g at STP), corresponds to 2.2 H2O molecules per formula unit, which is close to the amount of 2 H2O molecules within one cell unit, as indicated by the crystal structure. The affinity for H2O is ascribed to the strong adsorbate−adsorbent interactions by hydrogen bonds.26 In contrast, almost no N2 and H2O sorption was observed for the dehydrated solid 5′ (Figure S5, Supporting Information). Luminescence Property. Inorganic−organic hybrid coordination complexes have been reported to have ability to adjust the emission wavelength of organic materials through incorporation of metal centers, especially for the d10 metal centers.27 2322



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Figure 6. (a) The coordination environment of Co(II) atom in 6 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A 1 − x, 0.5 + y, 0.5 − z, B −0.5 + x, y, 0.5 − z, C 0.5 + x, y, 0.5 − z, D 1 − x, −0.5 + y, 0.5 − z, E 1 − x, 1 − y, −z. (b) The 2D layer of Co(II)-pbea2−. (c) The 2D layer of Co(II)-H2L−. (d) The 3D framework of 6. (e) Schematic representation of the tetra-nodal (3, 4)-connected 3D network of 6 with (4·62·103)(4·62)(4·64·8)2 topology.

rigidity and then decreased the nonradiative energy loss.30 This suggests that 2 may be a good candidates for potential hybrid inorganic−organic photoactive materials. Magnetic Property. The Mn(II) atoms in 1 are linked by ox2− to give a [Mn(ox)] chain (Figure 1b), and thus magnetic interactions between Mn(II) mediated by ox2− can be expected; however, in 3−6 the Co(II) or Ni(II) atoms are connected by H3L/H2L− and dicarboxylate ligands which cannot mediate magnetic interactions. Therefore, the temperature dependence of magnetic susceptibilities of 1 was studied in the range of 300 to 1.8 K with a 2000 Oe applied magnetic field.31 The χMT vs T curve is shown in Figure 9. The χMT value at 300 K is 8.49 emu K mol−1 for 1, which is smaller than the expected value of 8.75 emu K mol−1 for two uncoupled Mn(II) ions. Along with the lowering temperature, the χMT values decrease slowly. The shape of the χMT versus T curve is the characteristic of

Complexes 1 and 3−6 with Mn(II), Co(II), and Ni(II) centers have different colors (Figure S1, Supporting Information) and are nonemissive. In this paper, the solid-state photoluminescent properties of complex 2 together with free H3L and H2pbdc have been investigated in the solid state at room temperature. As depicted in Figure 8, it can be seen that 2 exhibits an intense fluorescent emission at 410 nm upon excitation at 348 nm, while weak emissions at 408 nm (λex = 360 nm) and 390 nm (λex = 355 nm) were observed for free H3L and H2pbdc ligands, respectively. Therefore, the fluorescent emission observed in 2 may be tentatively assigned to the intraligand fluorescence since the free ligand exhibited a similar weak emission under the same condition.28 The enhancement of luminescence for 2 compared with the free ligand under the same conditions may mainly originate from the coordination interactions between the metal atom and the ligand,29 which enhanced its conformational 2323



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Figure 9. The χMT vs T plot for 1 (the red line shows the best fit to the model).

occurrence of antiferromagnetic coupling between the Mn(II) centers which is mainly resulted from the superexchange through the 1D oxalate bridged Mn(II) chain. The interchain magnetic interactions within the chain can be fitted to the isotropic Hamiltonian H = −2J∑SiSi+1. The analytical expression can be derived by Fisher32 for a one-dimensional Heisenberg chain of classical spins [S = 5/2].33 The best fit in the range of 50−300 K was obtained with values of g = 2.29 and J = −2.76 cm−1. The agreement factor R, defined as ∑[(χMT)obsd − (χMT)calcd]2/ ∑(χMT)2, is equal to 4.62 × 10−3. The negative value of J further confirms the existence of antiferromagnetic interactions in 1.

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CONCLUSION Six new coordination polymers with rigid tripodal 4-imidazole containing ligand 1,3,5-tri(1H-imidazol-4-yl)benzene (H3L) and a variety of dicarboxylates have been obtained and found to show different structures and topologies. The remarkable feature for the 4-imidazole containing ligand is the deprotonation which endows it rich coordination modes. Also the results further show that the combination of rigid N-donor ligand with carboxylate can provide a promising access to the rational construction of MOFs with specific structures and properties.

Figure 7. (a) N2 gas adsorption isotherm of 3′ at 77 K: filled shape, adsorption; open shape, desorption. (b) H 2O adsorption isotherm of 3′ at 298 K: filled shape, adsorption; open shape, desorption.

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ASSOCIATED CONTENT

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AUTHOR INFORMATION

S Supporting Information *

X-ray crystallographic file in CIF format, hydrogen bonding data (Table S1), solid state UV−visible spectra (Figure S1), TGA (Figures S2 and S4), PXRD data (Figure S3), and sorption isotherms (Figure S5). This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author

*Fax: 86 25 8331 4502. Tel: 86 25 8359 3485. E-mail: sunwy@ nju.edu.cn. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 91122001 and 21021062) and the National Basic Research Program of China (Grant No. 2010CB923303).

Figure 8. Excitation (left) and emission (right) spectra of 2. 2324



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