Syntheses - American Chemical Society

Article pubs.acs.org/crystal

Intriguing Architectures Generated from 1,4-Bis(3- or 4‑pyridyl)-2,3diaza-1,3-butadiene with Aromatic Dicarboxylates: Syntheses, Crystal Structures, and Properties Jie Zhou,‡ Lin Du,‡ Yong-Feng Qiao, Yan Hu, Bin Li, Lin Li, Xiao-Yuan Wang, Jing Yang, Ming-Jin Xie, and Qi-Hua Zhao* Key Laboratory of Medicinal Chemistry for Natural Resource Education Ministry, Department of Chemistry, Yunnan University, Kunming, 650091, P. R. China S Supporting Information *

ABSTRACT: Six new mixed-ligand coordination polymers, namely, [Zn(1,3-bdc)(3-bpdb)]n (1), {[Zn(1,3-bdc)(4-bpdb)]·2H2O}n (2), [Co(1,4-bdc)(3-bpdb)(H2O)2]n (3), [Ni(1,4-bdc)(3-bpdb)(H2O)]n (4), {[Co5(1,4-ndc)4(3-bpdb)(μ3-OH)2(H2O)2(DMF)2]·2H2O·CH3OH}n (5), and {[Zn2(1,4-ndc)2(3-bpdb)]·H2O}n (6), where 3-bpdb = 1,4-bis(3pyridyl)-2,3-diaza-1,3-butadiene, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3butadiene, 1,3-H2bdc = 1,3-benzenedicarboxylic acid, 1,4-H2bdc = 1,4benzenedicarboxylic acid, and 1,4-H2ndc = 1,4-naphthalenedicarboxylic acid, were synthesized under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that the structures of complexes 1 and 2 were isomorphic and exhibited two-dimensional (2D) double-layered sql nets. Complex 3 had an interesting 2D → three-dimensional (3D) inclined polycatenation net based on 44-sql subunits. Complex 4 featured an uncommon 3D 2-fold cds network, while complex 5 possessed a rare uninodal self-penetrating 10-connected pentacobalt-clusterbased ile-(36.434.53.62) framework. Complex 6 displayed a 2-fold interpenetrated 3D six-connected pcu topology. These different intriguing architectures indicated that the coordination behaviors of metal ions and the coordination modes, the position isomers of carboxylate, and different steric hindrances of aromatics played important roles in the construction of CPs; moreover, bpdb ligands with conformational freedom may affect the formation of the final architectures. The photoluminescence properties of 1, 2, and 6 in the solid state and the magnetic properties of 5 were studied. Moreover, thermal analysis, powder X-ray diffraction, infrared spectroscopy, and elemental analysis were also performed.

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INTRODUCTION

and even small changes can result in a remarkable diversity of both architectures and properties.5 An effective approach for performing reactions is using mixed ligands such as multicarboxylate and N-containing ligands in the same system.6 Given the strength and versatility of carboxylate groups in binding metal ions, multicarboxylate compounds that can be designed to have various shapes, sizes, and functionalities are the most widely used organic ligands for constructing CPs with diverse structures and properties. Furthermore, taking advantage of the complementarity or competition between carboxylate and pyridyl in coordination, multipyridyl bridging ligands have been used in combination with multicarboxylate ligands. This heterolinker approach has greatly contributed to the structural and topological diversity of CPs.7 With conformational freedom, the bis-pyridyl ligands 1,4bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpdb) and 1,4-bis(4-

The rational design and syntheses of coordination polymers (CPs) continue to attract enormous interest because of the endless possibilities and inexhaustible synthesis options for tailoring their structures and properties.1 In the realm of CPs, topology control is fundamental for determining the properties and applications of the crystalline materials. Accordingly, many intriguing topological types and associated interesting properties have been investigated in depth.2 However, despite the developments in the construction of a diverse topology of architectures, the prediction of the precise solid-state structure or the control of dimensionality of CPs remains a long-term challenge from the perspective of developing advanced crystalline materials.3 Many researchers have reported that the resultant structural frameworks are frequently influenced by various factors, such as medium, solution pH, temperature, geometric requirements of metal atoms, metal−ligand ratio, template, structure of connecting ligands, and nature of counteranions.4 Among these factors, spacer ligands are attracting substantial attention because they are highly tunable, © 2014 American Chemical Society

Received: November 13, 2013 Revised: January 25, 2014 Published: February 4, 2014 1175

dx.doi.org/10.1021/cg401692e | Cryst. Growth Des. 2014, 14, 1175−1183

Crystal Growth & Design

Article

Table 1. Crystal Data and Structure Refinement Summary for Complexes 1−6a complex empirical formula formula weight temperature (K) crystal system space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) volume (Å3) Z Dcalc (g cm−3) F(0 0 0) data/restraints/parameters goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data) largest diff peak/hole (e Å−3) a

1

2

3

4

5

6

C20H14N4O4Zn 439.72 298(2) triclinic P1̅ 8.2609(16) 10.149(2) 12.461(2) 112.995(2) 99.133(3) 99.881(3) 917.6(3) 2 1.591 448 3256/0/262 1.039 R1 = 0.0518 wR2 = 0.0870 R1 = 0.1096 wR2 = 0.1080 0.705, −0.618

C20H18N4O6Zn 475.75 298(2) triclinic P1̅ 8.4150(11) 10.1129(11) 14.677(2) 74.1740(10) 80.7420(10) 78.6730(10) 1170.6(3) 2 1.350 488 4156/0/280 1.058 R1 = 0.0534 wR2 = 0.1499 R1 = 0.0841 wR2 = 0.1738 0.830, −0.518

C20H18CoN4O6 469.31 298(2) monoclinic C2/c 20.8725(17) 8.9411(7) 11.4430(9) 90 114.0580(10) 90 1950.0(3) 4 1.599 964 1757/0/143 1.021 R1 = 0.0259 wR2 = 0.0721 R1 = 0.0274 wR2 = 0.0735 0.314, −0.411

C20H16N4Ni O5 451.08 298(2) monoclinic Pc 10.627(2) 6.2498(13) 17.169(3) 90 118.378(9) 90 1003.3(3) 2 1.493 464 4538/2/277 0.971 R1 = 0.0562 wR2 = 0.0791 R1 = 0.1097 wR2 = 0.0963 0.560, −0.359

C67H62Co5N6O25 1645.88 298(2) orthorhombic Pbca 16.2445(11) 16.4805(11) 25.7372(17) 90 90 90 6890.3(8) 4 1.587 3364 6182/0/478 1.040 R1 = 0.0449 wR2 = 0.1290 R1 = 0.0572 wR2 = 0.1385 0.952, −1.386

C36H24N4O9Zn2 787.33 298(2) monoclinic C2/c 18.2139(15) 11.7900(10) 16.5932(13) 90 111.3200(10) 90 1016.9(3) 4 1.575 1600 2963/0/232 1.035 R1 = 0.0278 wR2 = 0.0687 R1 = 0.0359 wR2 = 0.0737 0.399, −0.315

R1 = Σ ∥Fo| − |Fc∥/Σ |Fo|. wR2 = [Σw(Fo2 − Fc2)2/Σw(Fo2)2]1/2. through the Internet at http://www.iucr.org. Thermogravimetric analysis (TGA) data were collected on a simultaneous SDT thermal analyzer at a heating rate of 10 °C/min under a N2 atmosphere (N2 flow rate = 0.06 L/min). Solid-state fluorescence spectra were measured at room temperature on a Hitachi FL-7000 fluorescence spectrophotometer with excitation and emission slit widths of 5 nm. Variable-temperature susceptibility measurements of crystalline samples were performed on a Quantum Design MPMS-XL SQUID magnetometer. Diamagnetic corrections were made from Pascal’s constants, and an experimental correction for a sample holder was also applied. Synthesis of Complexes 1−6. [Zn(1,3-bdc)(3-bpdb)]n (1). A mixture of 3-bpdb (21.0 mg, 0.1 mmol), Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), 1,3-H2bdc (16.6 mg, 0.1 mmol), and H2O/DMF/MeOH (8 mL; 1:1:6, v:v:v) was placed in a 25 mL Teflon-lined stainless steel vessel, heated to 120 °C for 2 days, and then cooled to room temperature over 12 h. Yellow block crystals of 1 were obtained. Yield: 27.2 mg (62% based on ZnII). Elemental analysis (%): calcd for (C20H14N4O4Zn): C 54.63, H 3.21, N 12.74; Found: C 54.31, H 3.28, N 12.96. IR (KBr, cm−1): 3444 (br), 1612 (vs), 1548 (s), 1390 (vs), 1318 (w), 873 (w), 730 (m), 707 (m), 436 (w). {[Zn(1,3-bdc)(4-bpdb)]·2H2O}n (2). Complex 2 was synthesized similarly as 1, except that 3-bpdb (21.0 mg, 0.1 mmol) was replaced with 4-bpdb (21.0 mg, 0.1 mmol). Yellow block crystals of 2 were obtained. Yield: 19.3 mg (43% based on ZnII). Elemental analysis (%): calcd for (C20H18N4O5Zn): C 52.48, H 3.52, N 12.24; Found: C 52.11, H 3.56, N 12.52. IR (KBr, cm−1): 3444 (br), 1670 (s), 1617 (vs), 1563 (s), 1397 (vs), 1229 (w), 1091 (w), 733 (m), 707 (m), 521 (w). [Co(1,4-bdc)(3-bpdb)(H2O)2]n (3). Complex 3 was synthesized similary as 1, except that 1,3-H2bdc (16.6 mg, 0.1 mmol) and Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol) were replaced with 1,4-H2bdc (16.6 mg, 0.1 mmol) and Co(NO3)2·6H2O (29.1 mg, 0.1 mmol), respectively. Red block crystals of 3 were obtained. Yield: 37.1 mg (79% based on Co II ). Elemental analysis (%): calcd for (C20H18CoN4O6): C 51.18, H 3.87, N 11.94; Found: C 51.52, H 3.96, N 11.59. IR (KBr, cm−1): 3443 (br), 1634 (vs), 1500 (w), 1390 (vs), 1303 (w), 1194 (w), 1094 (w), 820 (w), 752 (m), 546 (m), 457 (w).

pyridyl)-2,3-diaza-1,3-butadiene (4-bpdb) have been justified as efficient and versatile organic building units for the construction of coordination architectures.8 However, these good candidates are rarely used in combination with multicarboxylate ligands.9 Hence, systematic research on the coordination chemistry of bpdb ligands is necessary for constructing novel framework structures and understanding topology control. On the basis of the aforementioned considerations, we believe that the simultaneity of bpdb ligands and aromatic dicarboxylate (1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid) can contribute to the formation of various architectures under the process of self-assembly. In the present work, we successfully applied this strategy and obtained six new CPs, namely, [Zn(1,3-bdc)(3-bpdb)]n (1), {[Zn(1,3-bdc)(4-bpdb)]·2H2O}n (2), [Co(1,4-bdc)(3-bpdb)(H2O)2]n (3), [Ni(1,4-bdc)(3bpdb)(H 2 O)] n (4), {[Co 5 (1,4-ndc) 4 (3-bpdb)(μ 3 -OH) 2 (H2O)2(DMF)2]·2H2O·CH3OH}n (5), and {[Zn2(1,4-ndc)2(3-bpdb)]·H2O}n (6). Their syntheses, crystal structures, topologies, thermal stabilities, photoluminescence, and magnetic properties were reported in this paper.

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EXPERIMENTAL SECTION

Materials and Physical Measurements. All analytical-grade chemicals and solvents were commercially available and used as received without further purification. 1,4-Bis(3-pyridyl)-2,3-diaza-1,3butadiene and 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene were prepared according to a previously reported procedure.10 Elemental analyses for C, H, and N were carried out with an Elementar Vario ELIII analyzer. Fourier-transform (FT) infrared (IR) spectra were recorded as KBr disks on an FTS-40 IR infrared spectrometer in the 4000−400 cm−1 region. The phase purity of the samples was investigated by powder X-ray diffraction (PXRD) measurements carried out on a Bruker D8-Advance diffractometer equipped with Cu Kα radiation (λ = 1.5406 Å) at a scan speed of 1°/min. Simulation of the PXRD patterns were performed using single-crystal data and processed with the Mercury v1.4 program available free of charge 1176



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Figure 1. (a) Coordination environment of the Zn(II) atom of 1 (symmetry codes: (A) x, y + 1, z; (B) x + 1, − y + 1, −z + 2; (C) x, y + 1, z; (D) x, y, z + 1). (b) Coordination environment of the Zn(II) atom of 2 (symmetry codes: (A) x, y + 1, z; (B) x + 1, − y + 2, − z; (C) x, y + 1, z; (D) x, y, z + 1). (c) A view of the 2D 44-sql layer in 1. (d) A view of the 2D 44-sql layer in 2. (e) Packing diagram in the space-filling model showing the interdigitating arrangement of the 2-D arrays in 1. Each color represents one 44-sql layer. (f) Packing diagram in the space-filling model showing the interdigitating arrangement of the 2-D arrays in 2, with each color representing one 44-sql layer (red represents guest water molecules). [Ni(1,4-bdc)(3-bpdb)(H2O)]n (4). Complex 4 was synthesized similarly as 1, except that 1,3-H2bdc (16.6 mg, 0.1 mmol) and Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol) were replaced with 1,4-H2bdc (16.6 mg, 0.1 mmol) and Ni(NO3)2·6H2O (29.1 mg, 0.1 mmol), respectively. Green block crystals of 4 were obtained. Yield: 17.1 mg (38% based on Ni II ). Elemental analysis (%): calcd for (C20H16N4NiO5): C 53.26, H 3.58, N 12.42; Found: C 52.81, H 3.27, N 12.05. IR (KBr, cm−1): 3403 (br), 1564 (s), 1429 (m), 1381 (vs), 807 (m), 754 (m), 694 (m), 564 (w). {[Co5(1,4-ndc)4(3-bpdb)(μ3 -OH)2(H 2O)2(DMF)2]·2H2 O·CH 3OH}n (5). A mixture of 3-bpdb (21.0 mg, 0.1 mmol), Co(NO3)2·6H2O (59.2 mg, 0.2 mmol) and 1,4-H2ndc (43.2 mg, 0.2 mmol), and H2O/DMF/ MeOH (8 mL, v:v:v 1:1:6) was placed in a 25 mL Teflon-lined stainless steel vessel, heated to 85 °C for 2 days, and then cooled to room temperature over 12 h. Red block crystals of 5 were obtained. Yield: 51.3 mg (78% based on CoII). Elemental analysis (%): calcd for (C67H62Co5N6O25): C 48.89, H 3.80, N 5.10; Found: C 49.15, H 3.51, N 4.83. IR (KBr, cm−1): 3363 (br), 1594 (s), 1415 (m), 1356 (s), 1258 (w), 786 m, 691 (w), 568 (w), 445 (w). {[Zn2(1,4-ndc)2(3-bpdb)]·H2O}n (6). Complex 6 was synthesized similarly as 5, except that Co(NO3)2·6H2O (58.2 mg, 0.2 mmol) was replaced with Zn(NO3)2·6H2O (59.4 mg, 0.2 mmol). Yellow block crystals of 6 were obtained. Yield: 59.8 mg (76% based on ZnII). Elemental analysis (%): calcd for (C36H24N4O9Zn2): C 54.91, H 3.07, N 7.12; Found: C 54.14, H 3.51, N 7.39. IR (KBr, cm−1): 3470 (br), 1625 (vs), 1409 (vs), 1360 (vs), 1258 (m), 781 (s), 695 (w), 567 (w). X-ray Crystallography. The selected single crystal with suitable dimensions was mounted on a glass fiber and used for X-ray diffraction analyses. Crystallographic data were collected at 298 K on a Bruker Smart AXS CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) using ω-scan technique. Cell parameters were retrieved using SMART software and refined with SAINT on all observed reflections.11 Data reduction was performed with SAINT software and corrected for Lorentz and polarization effects. Absorption corrections were applied with the program SADABS.11 All structures were solved by direct methods using SHELXS-9712 and refined on F2 by full-matrix least-squares procedures with SHELXL-97.13 All nonhydrogen atoms were located in different Fourier syntheses and finally refined with anisotropic displacement parameters. Hydrogen atoms attached to the organic moieties were either located from the difference Fourier map or fixed stereochemically. In the cases of complexes 2, 5, and 6, hydrogen atoms of the lattice water molecules were located in a difference map and fixed at those positions but their

Uiso values were refined. During refinement of 5, some thermal restraints (isor, delu, and simu) have been used on the unreasonable atom. Details of the crystallographic data collection and refinement parameters are summarized in Table 1. Main bond lengths and angles are presented in Table S1 in the Supporting Information. The topological analysis of the complexes was produced using the TOPOS program14 (see Cambridge Crystallographic Data Centre (Nos. 967958−967963) for the six complexes).

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RESULTS AND DISCUSSION Descriptions of the Crystal Structures of 1−6. [Zn(1,3bdc)(3-bpdb)]n (1) and {[Zn(1,3-bdc)(4-bpdb)]·2H2O}n (2). Both polymers 1 and 2 have an interesting 2D double-layered structure and crystallize in the triclinic system with the P1̅ space group. The asymmetric unit of 1 contains one Zn(II) atom, one 1,3-bdc2− anion, and one 3-bpdb ligand, while in 2, apart from the 4-bpdb instead of 3-bpdb, two uncoordinated water molecules are involved. In the complexes, each distorted octahedral Zn(II) center is coordinated by four equatorial O atoms and two axial N atoms originating from three 1,3-bdc2− and a pair of 3-bpdb/4-bpdb ligands (Figure 1a,b). The Zn−O and Zn−N bond lengths are all within the normal ranges.15 The two independent carboxylate groups in each 1,3-bdc2− ligand function as a chelated bidentate and a syn−syn bridge, respectively; thus, the adjacent Zn(II) centers are extended by the 1,3-bdc linkers to generate 1D ribbons along the b axis. The Zn···Zn distances separated by the 1,3-bdc2− linker are 7.58 Å for 1 and 7.50 Å for 2, and those for the dimeric unit bridged by a pair of carboxylate groups are 4.08 Å (1) and 4.13 Å (2). The ribbons are parallel to one another and are further linked by 3bpdb/4-bpdb ligands along the c axis to generate 2D doublelayered (4,4)-sql networks with the nearest ribbon−ribbon distances of ca. 8.16 and 15.46 Å for 1 and 2, respectively (Figure 1 panels c and d). Given the larger bridging length of the ligand (4-bpdb) in 2, guest water molecules are allowed in the framework. Calculations using PLATON show that the voids in complex 2 occupy 28.7% of the crystal volume (335.9 Å3 out of the 1170.6 Å3 unit cell volume).16 1177



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Figure 2. (a) Coordination environment of the Co(II) atom (symmetry codes: (A) − x + 1/2, − y + 1/2, − z; (B) −x + 1, −y, −z; (C) x − 1/2, y + 1/2, z; (D) −x + 1, −y + 1, −z + 1; (E) x − 1/2, y − 1/2, z − 1). (b) A view of the 2D 44-sql layer in 3. (c) Catenation through Hopf links in the diagonal−diagonal (d−d) arrangement in 3. (d) Schematic of the inclined polycatenation in 3.

Further investigation of the crystal packing reveals that these parallel sql nets are extended through a staggered disposition with the presence of interlayer aromatic stacking between the 1,3-bdc2− ligands through the edge phenyl rings (Figure 1, panels e and f). The centroid···centroid distances are 3.91 Å for 1 and 3.74 Å for 2. [Co(1,4-bdc)(3-bpdb)(H2O)2]n (3). Single-crystal X-ray analysis reveals that compound 3 crystallizes in the centrosymmetric monoclinic C2/c space group. The structure of 3 contains one cobalt atom, one 1,4-bdc2−, one 3-bpdb ligand, and two coordinated water molecules. As shown in Figure 2a, Co1 is located on a crystallographic inversion center and is in a slightly distorted CoN2O4 octahedron, with two carboxylate oxygen atoms from two 1,4-bdc2− anions and two water oxygen atoms at the equatorial plane (Co1−O1 = 2.062 (1) Å and Co1−O3 = 2.109(1) Å). Moreover, the axial position is occupied by two nitrogen atoms from two 3-bpdb molecules (Co1−N1 = 2.184(1) Å). Further expansion of the structure through the monodentate bridging 1,4-bdc2− anions and 3bpdb ligands creates a (4,4) rhomboid grid CP layer (Figure 2b). Within each layer, the rhomboid windows have dimensions of 12.75 × 11.35 Å with angles of 106.15° and 73.85° (defined by Co···Co distances and Co···Co···Co angles). The large size of the grids in the two individual (4,4) layers allows an interesting interpenetration to occur. The packing of the layers generates two sets of layers oriented toward two directions with the angle between the two sets of 76.95°. Further insight into one window of a layer reveals that each window is catenated with the other two windows from one layer in the other set through Hopf links in a diagonal−diagonal (d−d) arrangement (Figure 2 panels c and d).17 Thus, 3 displays an interesting 2D → 3D inclined polycatenation structure.18 [Ni(1,4-bdc)(3-bpdb)(H2O)]n (4). X-ray single-crystal diffraction analysis reveals that 4 crystallizes in the noncentrosymmetric monoclinic Pc. The asymmetric unit consists of one Ni(II) atom, one 1,4-bdc2− anion, one 3-bpdb ligand, and one coordinated water molecule. As illustrated in Figure 3a, Ni(II) ion has a distorted octahedral geometry, and the equatorial plane is built by three carboxylate−oxygen atoms from two

Figure 3. (a) Coordination environment of the Ni(II) atom of 4. All hydrogens are omitted for clarity (symmetry codes: (A) − x + 1/2, − y + 1/2, − z; (B) −x + 1, −y, −z; (C) x−1/2, y + 1/2, z; (D) −x + 1, −y + 1, −z + 1; (E) x − 1/2, y − 1/2, z − 1). (b) 1D zigzag chain generated by 1,4-bdc linked Ni(II) centers. (c) 3-bpdb ligands linked zigzag chain in two directions with ABAB fashion. (d) 3D architecture of 4. (e) Topological representation of the 3D cds topology of 4 with 2-fold interpenetration.

independent 1,4-bdc2− and one water molecule, with the average value of Ni−Oeq bonds length being 2.051 Å. Two nitrogen atoms from two 3-bpdb ligands occupy the axial positions, with the mean value for the Ni−N3‑bpdb bonds length being 2.092 Å. The two independent carboxylate groups in each 1,4-bdc ligand function as a chelated bidentate and a monodentate bridge, respectively. Thus, the adjacent Ni(II) centers are 1178



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six oxygen atoms originating from four 1,4-ndc2− anions, one hydroxyl group, and one DMF (Co3−O distances range from 1.9917(19) to 2.183(2) Å). All Co−O and Co−N bond lengths are comparable to those in the reported polynuclear cobalt complexes.21 In 5, two symmetry-related μ3-OH− groups (symmetry code: − x + 1, − y, − z + 1) connect five Co(II) atoms to form a [Co5(μ3-OH)2]8+ cluster subunit. Such a cluster is held together by eight carboxylate groups, thereby constituting the pentanuclear [Co5(μ3-OH)2(COO)8] cluster. Within the pentanuclear clusters, five Co(II) ions are totally coplanar with Co···Co distances of 3.125 Å (Co1···Co2), 3.673 Å (Co2···Co3), and 3.079 Å (Co1···Co3). The pentanuclear clusters are then linked to 10 identical adjacent clusters by four (μ3-η2:η1)2-1,4-ndc2− (rose), four (η1)(μ2-η1:η1)-1,4-ndc2− (yellow), and two 3-bpdb ligands (blue) into a 3D framework (Figure 4b). In addition, uncoordinated water and methanol molecules are filed in framework pores. Calculations using PLATON show that the voids in 5 occupy 14.4% of the crystal volume (992.7 Å3 out of the 6890.3 Å3 unit cell volume). Topologically, each pentacobalt cluster can be defined as a 10-connected node, and the overall structure of 5 has a uninodal 10-connected self-penetrating ile-36.434.53.62 framework (Figure 4c). Notably, polymer 5 represents the highest connected uninodal self-penetrating network based on pentacobalt clusters.22 To the best of our knowledge, pentanuclear Co5-clusters usually serve as 6- or 8-connected nodes, and as 10-connected node forming a 3D framework is rare.23 To further understand this complicated structure of 5, the approach proposed by Schröder et al.24 to analyze highconnected frameworks is used here. In 5, Co(II) ions are linked by (μ3-η2:η1)2-1,4-ndc2− ligands to afford (4,4) networks. These (4,4) networks are cross-linked by (η1)(μ2-η1:η1)-1,4-ndc2− ligands which act as zigzag chains, and the zigzag chains in the interlayer region bridges across the diagonal of a single window in the (4,4) network. Consequently, the well-known eight-connected bcu net forms. Moreover, the 3-bpdb ligands link the nodes to complete the self-penetrating 10-connected ile framework of 5, as shown in Figure 5. {[Zn2(1,4-ndc)2(3-bpdb)]·H2O}n (6). Compound 6 crystallizes in the centrosymmetric monoclinic C2/c space group. The crystallographically unique Zn(II) atom has a square pyramidal coordination geometry (τ = 0.053)25 surrounded by four oxygen atoms from different 1,4-ndc2− ligands in the equatorial plane and a nitrogen atom from 3-bpdb at the axial position (with average values for Zn−Oeq bonds of 2.042 Å and Zn− N3‑bpdb bond length of 2.043 Å). Four carboxylate groups from different 1,4-ndc ligands form bridges between the two Zn(II) centers, thereby generating a paddle-wheel dimer [Zn2(CO2)4]. Each dinuclear unit has a crystallographic inversion center at the center of Zn−Zn cores. These dimers are connected by naphthalene rings to build 2D rhombic-grid (4,4) layers (Figure 6a). These 2D sheets are further connected together in the third dimension by axially coordinating 3-bpdb ligands to give a 3D open framework (Figure 6b) that possesses largely distorted cubelike cavities approximately 10.48 × 10.48 × 16.15 Å3 in size (Figure 6c). Topologically, if one considers the barycenters of paddle-wheel [Zn2(CO2)4] motifs to be six-connected nodes, the single net would then be rationalized as a familiar elongated pcu net. The two identical pcu nets are further interpenetrated in 2-fold mode (Figure 6d). In addition, the effective free volume (9.7%, 323.0 Å3 out of the 3319.4 Å3 unit cell volume)

extended by the 1,4-bdc linkers to generate 1D zigzag chains with Ni···Ni separations of 10.76 Å and an angle of 124.6° (defined by the 1,4-bdc/1,4-bdc angle), as illustrated in Figure 3b. These zigzag chains are bridged at Ni(II) atoms by 3-bpdb ligands that span in two directions in an ABAB fashion to generate 3D architecture (Figure 3, panels c and d). From the topological point of view, the structure of complex 4 can be represented as a uninodal, four-connected cds-65.8 net. The two identical cds nets are further interpenetrated in 2fold mode (Figure 3e). It would be expected that the cds CPs easily tend to be interpenetrated;19 however, of the previously reported ones, most of them are non-interpenetrated.20 {[Co 5 (1,4-ndc) 4 (3-bpdb)(μ 3 -OH) 2 (H 2 O) 2 (DMF) 2 ]·2H 2 O· CH3OH}n (5). Single-crystal X-ray analysis reveals that compound 5 crystallizes in the orthorhombic Pbca. The asymmetry unit of compound 5 consists of two and a half Co(II) ions, two 1,4-ndc2− anions, one-half 3-bpdb, one hydroxyl group, one coordinated water, as well as one DMF molecule, one uncoordinated water, and one-half methanol molecule. All Co(II) atoms have octahedral coordination spheres. As shown in Figure 4a, Co1 sitting on an inversion

Figure 4. (a) Coordination environments of Co(II) and the pentanuclear Co(II) cluster of 5 (symmetry codes: (A) −x + 1, −y, −z + 1; (B) −x + 1, −y + 1/2, −z + 1/2; (C) x − 1/2, −y + 1/2, −z + 1; (D) −x + 1/2, y − 1/2, z). (b) Linkages of pentacobalt cluster with 10 adjacent cores. (c) Schematic of the 10-connected self-penetrating net framework of ile-(36.434.53.62) topology.

center is coordinated by four oxygen atoms from four different 1,4-ndc molecules (Co1−O5 = 2.1302(19) Å and Co1−O8 = 2.2337(19) Å) and two coordinated hydroxyl group oxygen atoms (Co1−O10 = 1.9917(19) Å). Co2 is surrounded by three oxygen atoms of 1,4-ndc, one nitrogen atom of 3-bpdb, one coordination water molecule, and one hydroxyl group oxygen atom (Co2−O distances range from 1.9917(19) to 2.183(2) Å, and Co2−N1 = 2.136(3) Å). Co3 is surrounded by 1179



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Scheme 1. Different Coordination Modes of Dicarboxylate Ligands, with (a) for 1 and 2, (b) for 3, (c) for 4, (d) for 5, and (e) for 6, respectively

2) to 2D → 3D inclined polycatenation framework (3). Obviously, the position discrimination of the carboxylate ligands leads to the structural difference of 1 (or 2) and 3. Regarding 3 and 5, the two kinds of dicarboxylate (1,4-bdc2− in 3, 1,4-ndc2− in 5) with different coordination fashions and different steric hindrances result in totally different architectures. Furthermore, the choice of metal centers also significantly affects the conformation of bpdb, the binding fashions of dicarboxylate ligands, and the resultant extended networks of CPs. For example, under similar reaction conditions with only the change of Co(II) ions in 3 with Ni(II) ions in 4, the binding fashion of 1,4-bdc2− changes from μ2-κ2O:O′ (3) to μ2-κ3O:O′:O″ (4) and one bridging direction of 3-bpdb ligand (3) to two directions (4). Ultimately, completely different frameworks are formed. When considering 5 and 6, the same bridging ligands with different metal centers (Co(II) in 5 and Zn(II) in 6), resulting in 10-connected ile framework of 5 and 2-fold interpenetrated pcu network of 6. In addition, bpdb ligands with conformational freedom are also important in the assembly process of the terminal structures of the complexes. Notably, the two pyridyl rings of 3-bpdb are coplanar in complexes 2, 4, and 5, but form a dihedral angle of 14.1° in 3 and 54.6° in 6 through the rotation of the diaza group R−CN−NC−R (Scheme 2).

Figure 5. (a) The (4,4) network where pentanuclear Co(II) clusters are linked by (μ3-η2:η1)2-1,4-ndc2− ligands (pink). (b) Zigzag-chains from (η1)(μ2-η1:η1)-1,4-ndc2− (yellow) pentacobalt clusters. (c) Pentanuclear cobalt clusters linked by 1,4-ndc2− ligands. (d) The bcu network. (e) The 10-connected self-penetrating structure of 5 where 3-bpdb ligands are shown in blue. (f) The ile network.

Scheme 2. Representation of the Conformation Flexibility of 3-bpbd

PXRD Results. To determine whether the crystal structures are truly representative of the bulk materials tested in property studies, PXRD experiments were carried out for compounds 1− 6. The PXRD experimental and as-simulated patterns of compounds 1−6 are shown in the Supporting Information (Figure S2). The bulk synthesized materials and the measured single crystals for 1−6 are found to be the same. Thermogravimetric Analysis (TGA). To characterize the thermal stabilities of complexes 1−6, their thermal behaviors were investigated under nitrogen atmosphere at a heating rate of 10 °C min−1 by TGA (Figure S3, Supporting Information). Complex 1 remains stable up to ca. 360 °C, finally leading to the formation of the stoichiometric amount of ZnO as a residue (obsd 21.88%, calcd 18.50%). The TG curve for 2 shows a gradual weight loss between 60 and 194 °C, which can be ascribed to the removal of lattice water molecules (obsd 8.60%, calcd 7.57%). The removal of organic ligands occurs within the range of ca. 315−493 °C. The remaining weight corresponds to the formation of ZnO (obsd 19.56%, calcd 17.11%). For 3, the

Figure 6. (a) View of the (4,4) layer. (b) View of a single 3D framework pillared by 3-bpdb ligands. (c) A distorted cubelike cage in 6. (d) Schematic of the 2-fold interpenetrating pcu net.

remains even after interpenetration and becomes occupied by uncoordinated water molecules. Structural Diversity of CPs 1−6. As discussed above, the six CPs exhibit different framework structures. Generally, the diverse structures are mainly attributed to the different inorganic building blocks and various coordination modes and conformations of the two kinds of ligands. First of all, the dicarboxylate ligands with different geometry and binding fashions are undoubtedly an important factor influencing the CP structures (Scheme 1). For example, with regard to 1 (or 2) to 3, the frameworks change from double-layered sql net (1 or 1180



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Figure 7. (a) Temperature dependence of χMT (Δ), χM (○), and χM−1 (□, inset) product at 1000 Oe for complex 5. The solid line corresponds to the theoretical fit of the Curie−Weiss law χM = C/(T − θ). (b). Field dependence of magnetization for 5 at 2 K. Inset: Temperature dependence of the real (χ′) and imaginary components (χ″) of the ac susceptibilities of 5 under a zero-static magnetic field.

initial weight loss between 160 and 210 °C is attributed to the release of coordinated water molecules (obsd, 7.87%; calcd, 7.67%). The decomposition of the anhydrous composition starts at 246 °C. The remaining weight beyond 454 °C corresponds to the formation of ZnO (obsd 17.46%, calcd 15.96%). For 4, the departure of coordinated water molecule is observed within the range of ca. 70−230 °C (obsd, 4.37%; calcd, 3.99%), and the decomposition of the compound occurs at ca. 345 °C with NiO residue (obsd, 18.50%; calcd, 16.56%). For 5, the gradual weight loss within the range of ca. 72−110 °C is attributed to the release of lattice water and methanol molecules (obsd, 4.45%; calcd, 4.31%). The departure of coordinated water and DMF molecules is observed within the range of ca. 110−350 °C (obsd, 16. 11%; calcd, 16.54%). Afterward, the resulting porous framework begins to decompose. The residue of 24.73% beyond 435 °C is assigned to cobalt oxide residue (calcd, 22.76%). For 6, the weight loss within the range of 75−150 °C is attributed to the release of lattice water (obsd, 2.54%; calcd, 2.29%), and the decomposition of the compound occurs at ca. 300 °C with ZnO residue (obsd, 21.80%; calcd, 20.67%). Photoluminescence Properties. CPs constructed from d10 metal centers and conjugated organic linkers are promising candidates for hybrid photoactive materials with potential applications because of their higher thermal stability and controllable photoluminescence properties. The emission spectra of 1, 2, and 6, as well as 4-bpdb and 3-bpdb ligands, were examined in the solid state at room temperature (Figure S4, Supporting Information). The dicarboxylate ligands 1,3H2bdc (λem = 370 nm),15c and 1,4-H2ndc (λem = 508 nm)22b can also exhibit fluorescence at room temperature (Figure S5, Supporting Information). The fluorescent emission of 1 is similar to that of 6. Excitation at 375 nm leads to three intense fluorescent emission bands with the peak at ca. 472/486/495 nm for 1 and 6. Additionally, their emission spectra display a similar shoulder peak at 530 nm. Complex 2 displays a broad band with the peak maximum at 530 nm and three shoulder peaks at ca. 472, 486, and 494 nm upon excitation at 375 nm. The emissions of 1, 2, and 6 are neither metal-to-ligand charge transfer (MLCT) nor ligand-to-metal charge transfer (LMCT) in nature since the ZnII ion is difficult to oxidize or to reduce due to its d10 configuration,26 and the emissions can potentially be assigned to the π* → π transitions of bis-pyridyl ligands because similar peaks also appear for free 3-bpdb and 4-bpdb.9b Magnetic Properties of Polymer 5. Variable-temperature magnetic susceptibility measurements were performed on powdered crystalline samples of complex 5 at 1000 Oe field

within the 2−300 K range. The obtained data for complex 5 is shown as χM−1 (inset), χM, and χMT versus T plots in Figure 7a. χMT is equal to 14.93 cm3 mol−1 K at 300 K, which is much larger than the expected value of 9.38 cm3 mol−1 K for an uncoupled system for five CoIII ions (g = 2, S = 3/2) because of the significant spin−orbital coupling of CoII centers. Upon cooling, χMT monotonously decreases to achieve the minimum value of 2.68 cm3 mol−1 K at 2 K, suggesting an appreciable antiferromagnetic exchange between Co(II) ions connected through two μ3−O and O−C−O bridges. According to the plot of χM−1 vs T, the magnetic behavior of both complexes follow the Curie−Weiss law χM = C/(T − θ) from approximately 25 to 300 K, with a Curie constant C value of 8.98 cm3 K mol−1 and a Weiss temperature θ of −59.99 K. This behavior reveals the characteristic of a system with dominant antiferromagnetic interactions between Co(II) ions and the presence of spin− orbit couplings. Despite the 3D structural features, complex 5 can be magnetically described as an isolated 0D Co5-cluster because the large Co5···Co5 separation across 1,4-ndc2− and 3bpdb spacers exclude an efficient direct exchange between Co5clusters. To probe the low-temperature magnetic properties of 5, isothermal field-dependent magnetizations M(H) and ac susceptibility measurements were performed (Figure 7b). Magnetization of this complex per Co5 unit at 2.0 K reaches 3.53 Nβ at 70 kOe without achieving saturation. In addition, no frequency-dependence and peaks are found in the in- and out of-phase ac susceptibility signals at 2.0 K. Thus, compound 5 is not a single-molecule magnet.

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CONCLUSIONS Through a synthesis route of combining a mixed ligand of dicarboxylate (1,3-H2bdc, 1,4-H2bdc, and 1,4-H2ndc) and Ndonor ligands (3-bpdb and 4-bpdb), two 2D double-layered sql nets (1 and 2), an interesting 2D → 3D inclined polycatenation framework (3), a 2-fold interpenetrated 3D network with cds topology (4), a rare uninodal self-penetrating 10-connected ile framework (5), and a 2-fold interpenetrated 3D network with pcu topology (6), have been obtained. Results indicate that the coordination behaviors of metal ions, the dicarboxylate ligands, as well as the bpdb ligands show significant effects on the formation of the final structures. This work prompts us to achieve more functional crystalline solids through such a reliable synthesis route using mixed-ligand bpdb and other aromatic multicarboxylate ligands as spacers. Efforts on this perspective are currently underway. 1181



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ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic information for 1−6 in CIF format, tables of selected bond parameters, IR spectra, TGA plots, and PXRD patterns for 1−6. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Fax: +86-871-65035640 E-mail: [email protected]. Author Contributions ‡

J.Z. and L.D. contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Projects 21061016 and 21371151) and Scholarship Award for Excellent Doctoral Student granted by Yunnan Province.

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