Seven Coordination Polymers Derived from Semirigid Tetracarboxylic

Mar 27, 2015 - 1HNMR (400 MHz, DMSO-d6): δ 13.32 (s, br, 4H), 8.26 (t, 2H), 7.68 (d, 3H), ..... wR2 = |Σw(|F0|2 – |Fc|2)|/Σ|w(F0)2|1/2, where w =...
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Seven Coordination Polymers Derived from Semirigid Tetracarboxylic Acids and N‑Donor Ligands: Topological Structures, Unusual Magnetic Properties, and Photoluminescences Chang-Dai Si,† Dong-Cheng Hu,† Yan Fan,† Yu Wu,† Xiao-Qiang Yao,† Yun-Xia Yang,† and Jia-Cheng Liu*,†,‡ †

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People’s Republic of China State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China

‡

S Supporting Information *

ABSTRACT: Seven new complexes based on H4L1 and H4L2, namely, [Cd2(L1)(H2O)5]n (1), {[Cu5(L1)2(μ3-OH)2(H2O)4]·2H2O}n (2), {[Cd2(L1)(4,4′-bipy)2(H2O)3]·2H2O}n (3), [Zn2(L1)(4,4′-bipy)(H2O)3]n (4), {[Ni7(L1)4(4,4′-bipy)12(H2O)12]·2H2O}n (5), {[Ni1.5(L2)(4,4′-bipy)1.5(H2O)4]·H2O}n (6), and {[Ni 9 (L 2 ) 6 (dib) 1 2 (H 2 O) 1 8 ]·18H 2 O} n (7) [(H 4 L 1 = 4-(3′,5′dicarboxylphenoxy)phthalic acid, H4L2 = 3-(3′,5′-dicarboxylphenoxy)phthalic acid, 4,4′-bipy = 4,4′-bipyridine, dib = 1,4-di(1H-imidazol-1-yl)benzene], have been synthesized by solvothermal reactions. Complex 1 possesses a 4-connected chiral three-dimensional (3D) structure with a Schläfli symbol of (4.63.82). Complex 2 presents a (4,6)-connected porous architecture based on a chairshaped [Cu4(μ3-OH)2]6+ secondary building unit (SBU) with a Schläfli symbol of (43.63)2(46.66.83), revealing unusual ferromagnetic behavior. Complex 3 exhibits a 2D → 3D framework through H-bonding interactions, which is a (3,3,4)-connected 2-fold interpenetrated structure with a Schläfli symbol of (6.82)2(63.83). Complex 4 shows a (3,4,6)-connected (4.64.8)2(62.8)2(42.66.86.10) topology. Complex 5 displays a rare (3,4)connected polycatenation structure, possessing identical topologies with a Schläfli symbol of (63)(65.8) and weakly ferromagnetic behavior. Complex 6 features a (3,4)-connected 3D framework with a Schläfli symbol of (4 × 102)2(42.103.12). Complex 7 can be regarded as a (4,4)-connected (63.83)2(85.10) topology. Moreover, diverse structural topologies have not been documented hitherto. The magnetic properties of 2 and 5 are discussed in detail. The fluorescence properties have also been analyzed with density functional theory calculations, indicating that the emissions can be ascribed to intraligand charge transfer for 1 and ligandto-ligand charge transfer for 3−4.

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modes and flexible molecular backbones can provide a variety of coordination polymers with appealing structures and properties.10 So far many various coordination polymers with intriguing topologies have been fabricated by using semirigid ligands as linkers, such as 5-(4-carboxybenzyloxy)-isophthalic acid,11 5-(4-carboxy-phenoxy)-isophthalic acid,12 4-(4-carboxyphenoxy)-phthalic acid,13 3-[(3′,4′-dicarboxyphenyl)thio]phthalic acid, 3-[(2′,3′-dicarboxyphenyl)thio]phthalic acid,14 2,2′,3,3′-oxidiphthalic acid,15 and 4,4′-oxidiphthalic acid.16 The usage of the m-benzenedicarboxylate subunit for the construction of CPs has been extensively researched.17 However, 4(3′,5′-dicarboxyl-phenoxy)phthalic acid (H4L1) and 3-(3′,5′dicarboxylphenoxy)phthalic acid (H4L2) containing one mbenzenedicarboxylate moieties with different spacers are rare to construct novel CPs. In addition, most semirigid ligands can be easily prepared by the cross-coupling reactions such as Suzuki

INTRODUCTION Coordination polymers (CPs) have gotten great attention in crystal engineering owing to their potential applications in various fields such as luminescence,1 gas storage and separation,2 catalysis,3 ion exchange,4 toxic gas removal,5 topological insulators,6 and magnetism.7 To date, how to rationally design and synthesize CPs with the expected structure and properties is still faced with many difficulties, because the structure of CPs may be easily affected by organic ligands, metal ions, solvent, reaction temperature, counterions, etc.8 The first of them may be organic ligands, which play a crucial role in constructing new CPs, and the second may be metal ions, followed by solvent, temperature, etc. Certainly three-dimensional (3D) printing techniques may be used to optimize the synthesis conditions, resulting in the discovery of many new coordination polymers in the future.9 Up to now, organic ligands with carboxylate groups have been widely used to build fascinating structures. Compared to rigid and flexible carboxylate ligands, semirigid multicarboxylate ligands are of special interest because their varied coordination © XXXX American Chemical Society

Received: February 10, 2015 Revised: March 25, 2015

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DOI: 10.1021/acs.cgd.5b00205 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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of 4-nitrophthalonitrile with a yield of 2.07 g (85.3%). IR (KBr, cm−1): 3424(s), 1695(s), 1649(m), 1582(s), 1456(w), 1377(s), 1266(m), 1070(s), 945(w), 761(s). 1HNMR (400 MHz, DMSO-d6): δ 8.16 (s, 1H), 7.80 (d, 1H), 7.52 (d, 3H), 7.29 (d, 1H). Synthesis of [Cd2(L1)(H2O)5]n (1). Cd(NO3)2·4H2O (0.040 g, 0.13 mmol), H4L1 (0.0259 g, 0.075 mmol), DMF (2 mL), and H2O (6 mL) were added in a Teflon-lined autoclave and heated to 130 °C for 60 h, and then cooled to room temperature. Colorless block-shaped crystals of 1 were obtained in 48% yield (based on H4L1), washed with water and air-dried. Anal. Calcd for C16H16O14Cd2 (657.09): C, 29.24; H, 2.45%. Found: C, 29.04; H, 2.35%. IR (KBr, cm−1): 3453(s), 1612(w), 1549(s), 1387(s), 1256(s), 1209(w), 1150(w), 997(m), 832(w), 780(m). Synthesis of {[Cu5(L1)2(μ3-OH)2(H2O)4]·2H2O}n (2). The preparation of 2 was similar to that of 1, except that CuSO4·5H2O was used. Blue plate-shaped crystals of 2 were obtained in 46% yield (based on H4L1), washed with water and air-dried. Anal. Calcd for C32H30O26Cu5 (1155.52): C, 33.26; H, 2.62%. Found: C, 33.48; H, 2.58%. IR (KBr, cm−1): 3118(m), 1615(w), 1569(s), 1455(w), 1380(s), 1261(m), 1215(m), 1163(s), 1036(m), 985(s), 801(m), 724(m). Synthesis of {[Cd2(L1)(4,4′-bipy)2(H2O)3]·2H2O}n (3). The preparation of 3 was similar to that of 1, except that 4,4′-bipy was used. Colorless block-shaped crystals of 3 were obtained in 45% yield (based on H4L1), washed with water and air-dried. Anal. Calcd for C36H32N4O14Cd2 (969.46): C, 44.60; H, 3.33; N, 5.78%. Found: C, 44.75; H, 3.42; N, 5.70%. IR (KBr, cm−1): 3311(s), 1609(m), 1553(s), 1392(s), 1257(m), 1211(m), 1070(m), 1003(m), 817(s), 734(m). Synthesis of [Zn2(L1)(4,4′-bipy)(H2O)3]n (4). The preparation of 4 was similar to that of 3 except that Zn(NO3)2·6H2O was used instead of Cd(NO3)2·4H2O. Colorless needle-shaped crystals of 4 were obtained in 46% yield (based on H4L1), washed with water and airdried. Anal. Calcd for C26H20N2O12Zn2 (683.18): C, 45.71; H, 2.95; N, 4.10%. Found: C, 45.65; H, 2.90; N, 4.05%. IR (KBr, cm−1): 3223(s), 1585(m), 1542m), 1370(s), 1257(m), 1211(m), 1070(m), 997(m), 820(m), 776(s). Synthesis of {[Ni7(L1)4(4,4′-bipy)12(H2O)12]·2H2O}n (5). The preparation of 5 was similar to that of 4 except that Ni(OAc)2·4H2O was used instead of Zn(NO3)2·6H2O. Green block-shaped crystals of 5 were obtained in 46% yield (based on H4L1), washed with water and air-dried. Anal. Calcd for C124H104N12O52Ni7 (3005.16): C, 49.56; H, 3.42; N, 5.60%. Found: C, 49.21; H, 3.39; N, 5.98%. IR (KBr, cm−1): 3393(m), 3226(m), 1694(m), 1609(m), 1536(s), 1373(s), 1254(m), 1214(m), 1070(w), 994(m), 823(m), 779(m). Synthesis of {[Ni1.5(L2)(4,4′-bipy)1.5(H2O)4]·H2O}n (6). The preparation of 6 was similar to that of 5 by using L2 in place of L1. Blue blockshaped crystals of 6 were obtained in 51% yield (based on H4L2), washed with water and air-dried. Anal. Calcd for C31H29N3O14Ni1.5 (755.64): C, 49.22; H, 3.84; N, 5.56%. Found: C, 49.78; H, 3.80; N, 5.51%. IR (KBr, cm−1): 3409(w), 3164(s), 1676(m), 1612(w), 1553(s), 1462(m), 1389(s), 1306(s), 1226(m), 1134(m), 997(m), 813(m), 774(s). Synthesis of {[Ni9(L2)6(dib)12(H2O)18]·18H2O}n (7). Complex 7 was prepared in a similar procedure as 6 by using dib in place of 4,4′-bipy. Blue block-shaped crystals of 7 were obtained in 41% yield (based on H 4 L 2 ), washed with water and air-dried. Anal. Calcd for C240H232N48O90Ni9 (5757.13): C, 50.07; H, 4.06; N, 11.68%. Found: C, 50.28; H, 4.10; N, 11.81%. IR (KBr, cm−1): 3424(s), 3128(w), 1609(w), 1562(w), 1531(s), 1444(w), 1381(s), 1307(m), 1247(s), 1136(w), 1069(s), 954(m), 832(m), 772(m). Infrared Spectroscopy. The IR spectra of complexes 1−7 show characteristic bands of the coordinated carboxylate groups at 1612, 1549 cm−1; 1615, 1569 cm−1; 1609, 1553 cm−1; 1585, 1542 cm−1; 1609, 1536m−1; 1612, 1553 cm−1; 1609, 1562 cm−1 for asymmetric stretching vibrations, respectively. The absorption bands at 1387 cm−1, 1380 cm−1, 1392 cm−1, 1370 cm−1, 1373 cm−1, 1389 cm−1, and 1381 cm−1 for 1−7, respectively, are attributed to the symmetric stretching vibrations of the coordinated carboxylate groups.21 The (νas − νs) values (162/225 cm−1 for 1, 189/235 cm−1for 2, 161/217 cm−1 for 3, 172/215 cm−1 for 4, 163/236 cm−1 for 5, 164/223 cm−1 for 6, 181/

coupling, and the Sonogashira coupling reaction.18 Enlightened by the aforementioned considerations, two semirigid tetracarboxylate ligands, H 4 L 1 and H 4 L 2 , were designed and synthesized for the first time (Scheme 1). On the other hand, Scheme 1. Molecular Structures of H4L1 and H4L2

the N-donor ligands have also been proven to be effective building units to adjust the coordination mode of polycarboxylate acid.19 Herein, we successfully obtained seven new coordination polymers based on two semirigid tetracarboxylate and N-donor ligands, namely, [Cd 2 (L 1 )(H 2 O) 5 ] n (1), {[Cu5(L1)2(μ3-OH)2(H2O)4]·2H2O}n (2), {[Cd2(L1)(4,4′bipy)2(H2O)3]·2H2O}n (3), [Zn2(L1)(4,4′-bipy)(H2O)3]n (4), {[Ni7(L1)4(4,4′-bipy)12(H2O)12]·2H2O}n (5), {[Ni1.5(L2)(4,4′bipy)1.5(H2O)4]·H2O}n (6), and {[Ni9(L2)6(dib)12(H2O)18]· 18H2O}n (7). Their syntheses, structures, and magnetic and luminescent properties are discussed in detail.

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EXPERIMENTAL SECTION

Materials and Instrumentations. Other reagents and solvents were purchased and used without further purification. 1HNMR (400MHz) was measured on a Varian Mercury Plus-400 spectrometer. Elemental analyses of C, H, and N were performed on a VxRio EL Instrument. Fourier transform infrared (FT-IR) spectra were recorded in the range 4000−400 cm−1 on an FTS 3000 (the United States DIGILAB) spectrometer using KBr pellets. Thermogravimetric analysis (TGA) experiments were carried out on a PerkinElmer TG7 analyzer heated from 25 to 800 °C at a heating rate of 10 °C/min under N2 atmosphere. Powder X-ray diffraction (PXRD) patterns were obtained on a Philips PW 1710-BASED diffractometer at 293 K. The luminescence spectra were carried out on LS-55 (PE USA Inc.) fluorescence spectrophotometer at room temperature. Magnetic susceptibility data were obtained on microcrystalline samples, using a Quantum Design MPMS(SQUID)-XL magnetometer. Syntheses of H 4 L 1 and H 4 L 2 . The ligand of 4-(3′,5′dicarboxylphenoxy)phthalic acid (H4L1) was synthesized according to the following procedure.20 To a solution of 5-hydroxy-isophthalic acid diethyl ester (1.68 g, 8.0 mmol) and anhydrous NaOH (0.4 g, 10 mmol) in DMF (20 mL) stirred for 30 min, 4-nitrophthalonitrile (1.38 g, 8.0 mmol) was added. The resulting mixture was stirred for 24 h at 50 °C under nitrogen atmosphere. Then the mixture was poured into water of 2 °C approximately (200 mL), and a slightly yellow solid was yielded and isolated by filtration. The product was washed by water and dried in air, yielding dimethyl 5-(3′,4′-dicyanophenoxy)isophthalate (2.35 g, 87.4%). The mixture of dimethyl 5-(3′,4′-dicyanophenoxy)isophthalate (2.35 g, 7.0 mmol), NaOH (4 mol/L, 55 mL), and ethanol (15 mL) was refluxed until emissions of ammonia ceased. The solution was then cooled down to room temperature and filtered. The pH value of the filtrate was adjusted to about 5.0 with HCl (4.0 mol/L), which was deposited at room temperature for about 24 h; the numerous white solid of H4L1 was collected by filtration and washed by acetone with a yield of 1.80 g (74.3%). IR (KBr, cm−1): 3427(s), 2950(m), 1738(s), 1594 (m), 1591 (w), 1450(m), 1373(s), 1279 (s), 1214(m), 1086(m), 984 (w), 768 (s), 687(m). 1HNMR (400 MHz, DMSO-d6): δ 13.32 (s, br, 4H), 8.26 (t, 2H), 7.68 (d, 3H), 7.20 (d, 1H). The preparation of H4L2 is similar to the above-described procedure except that 3-nitrophthalonitrile (1.38 g, 8.0 mmol) was used instead B

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Table 1. Crystal Data and Structure Refinement for Complexes 1−7

a

complex

1

2

3

4

5

6

7

formula F.W. cryst system space group a /Å b /Å c /Å α /° β /° γ /° V (Å3) Dc (g/cm3) Z F(000) 2θ max (deg) GOF R1 [I > 2σ(I)]a wR2b [I > 2σ(I)]b

C16H16O14Cd2 657.09 monoclinic C2 18.516(3) 7.9896(11) 16.502(2) 90 118.946(2) 90 2136.3(5) 2.043 4 1280 50 1.166 0.0388 0.1255

C32H24O26Cu5 1142.26 triclinic P1̅ 10.7643(4) 11.1903(5) 11.8805(6) 101.006(4) 110.549(4) 99.779(4) 1270.95(11) 1.492 1 569 57.2 1.055 0.0402 0.1191

C36H32N4O14Cd2 969.48 monoclinic P21/n 21.1595(6) 10.0443(2) 16.9449(4) 90 100.237(2) 90 3544.01(15) 1.817 4 1936 52.0 1.058 0.0375 0.0930

C26H20N2O12Zn2 683.22 monoclinic P21/n 7.6683(5) 41.941(3) 7.8187(6) 90 104.516(8) 90 2434.4(3) 1.864 4 1384 52.0 1.05 0.0431 0.1005

C124H104N12O52Ni7 3005.02 triclinic P1̅ 10.0879(7) 11.3386(8) 28.2595(16) 89.390(5) 81.837(5) 87.109(6) 3195.6(4) 1.561 1 1544 50 1.08 0.0604 0.1551

C31H29N3O14Ni1.5 6045.10 monoclinic C2/c 37.359(2) 7.7625(2) 22.3426(7) 90 91.094(4) 90 6478.2(4) 1.549 4 3120.0 52.0 1.047 0.0412 0.1045

C240H232N48O90Ni9 5757.13 triclinic P1̅ 8.7712(5) 22.9092(17) 32.3091(14) 76.589(5) 89.490(4) 82.229(6) 6255.5(7) 1.528 1 2980 50 1.029 0.0723 0.1254

R1 = Σ∥F0| − |Fc∥/Σ|F0|. bwR2 = |Σw(|F0|2 − |Fc|2)|/Σ|w(F0)2|1/2, where w = 1/[σ2(F02) + (aP)2 + bP]. P = (F02 + 2Fc2)/3.

228 cm−1 for 7) are in accordance with the spectroscopic criteria of diverse carboxylate coordination modes.22 X-ray Crystallography. The crystallographic data collections for 1−7 were carried out on a Bruker Smart Apex CCD area detector diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 20(2) °C using ω-scan technique. The diffraction data were integrated by using the SAINT program,23a which was also used for the intensity corrections for the Lorentz and polarization effects. Semiempirical absorption corrections were applied using SADABS program.23b The structures were solved by direct methods, and all of the non-hydrogen atoms were refined anisotropically on F2 by the fullmatrix least-squares technique using the SHELXL-97 crystallographic software package.23c The hydrogen atoms except those of water molecules were generated geometrically and refined isotropically using the riding model. The details of the crystal parameters, data collection and refinements for the complexes are summarized in Table 1. Selected bond distances [Å] and angles [deg] are given in Table S1 (Supporting Information). Hydrogen bonds of 3 and 6 are listed in Table S2 (Supporting Information). CCDC 1038088 (1), 1031404 (2), 1031401 (3), 1031402 (4), 1031403 (5), 1031405 (6), and 1031406 (7) include all supplementary crystallographic data of seven complexes.

Figure 1. Coordination environment of 1 with 30% ellipsoid probability (hydrogen atoms and water molecules are omitted for clarity). Symmetry codes: A, 2 − x, y, 2 − z; B, 1.5 − x, 0.5 + y, 1 − z; C, 1.5 − x, 0.5 + y, 2 − z.

chains (Figure 2c). On the other hand, Cd2 ions are chelated by carboxylate groups in cis-cis-μ2-η1:η1 coordination modes, generating a left-handed helical chain (Figure 2b). Furthermore, the 1D helical chains and the 2D networks are connected by L14− ligands to form an elegant 3D framework, where Cd1 and Cd2 are alternately arranged in columns along the bc plane (Figure 2a). Topologically, both dinuclear Cd(II) secondary building unit (SBU) and L1 ligand are viewed as 4-connected nodes. The 3D structure of 1 belongs to a uninodal 4-connected net with a Schläfli symbol of (4.63.82), including a left-handed helical chain (Figure 3a). Crystal Structure of {[Cu5(L1)2(μ3-OH)2(H2O)4]·2H2O}n (2). Complex 2 exhibits a porous architecture based on tetranuclear SBUs and belongs to the triclinic system with space group P1.̅ The asymmetric unit of 2 consists of five CuII ions, two L1 ligands that adopt a μ7-η1:η0:η1:η1:η1:η1:η1:η1 coordination mode (Scheme S1b, Supporting Information), four coordinated water molecules, a pair of μ3-OH groups, and two lattice water molecules. As illustrated in Figure 4, Cu1 ion locates at the crystallographic inversion center and is four-coordinated by two O atoms (O1 and O1A) from two different ligands and two coordinated water molecules (O10W and O10WA) to form a regular square-planar CuO4 coordination geometry. Both Cu2 and Cu3 ions are five-coordinated geometry but exhibit two types of coordination environments. Cu2 ion is surrounded by

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RESULTS AND DISCUSSION Crystal Structure of {Cd2(L1)(H2O)5}n (1). Complex 1 crystallizes in the monoclinic with space group C2 and exhibits a 4-connected chiral 3D structure. The asymmetric unit consists of two independent CdII ions, one L1 ligand, and five coordinated water molecules. Cd1 ion is seven-coordinated in a distorted pentagonal bipyramid geometry by five O atoms of three individual L1 ligands and two O atoms of water molecules (Figure 1). Similarly to Cd1 ion, four carboxyl O atoms (O6, O7, O8B, and O14B) and one O atom (O12) of aqua ligands define the equatorial plane, while the distorted axial positions are occupied by O11 and O13 atoms, and the angle of O11− Cd2−O13 is 163.2(3)°. All Cd−O bond distances vary from 2.246(1) to 2.596(8) Å (Table S1, Supporting Information). L1 ligand, which can be regarded as a pentadentate ligand, coordinates Cd1 and Cd2 centers in a μ5-η1:η1:η1:η1:η1:η1:η1:η2 coordination mode (Scheme S1a, Supporting Information). L14− ligands linked Cd1 centers to form 1D ribbons along the b axis (Figure 2d). Besides, the 2D sheet-like structure was constructed via L14− ligands connecting with adjacent 1D C

DOI: 10.1021/acs.cgd.5b00205 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 2. (a) Schematic representation of 3D framework including 1D helical chains along the a axis. (b) View of a left-handed helical chain. (c) View of the 2D sheet. (d) Schematic drawing of the 1D ribbons.

between square pyramid and trigonal bipyramid. Cu3 ion is coordinated to three O atoms of three L14− ligands and two μ3hydroxo groups [Cu3−O12 = 1.992(6) Å, Cu3−O12D = 1.971(6) Å] (τ = 0.28 for Cu3),24 exhibiting a distorted squarepyramidal coordination geometry. Furthermore, the four CuII ions are bridged by a pair of μ3-OH groups to form a chairshaped [Cu4(μ3-OH)2]6+ SBU (Figure S1, Supporting Information). The intermetallic distance by the μ3-OH groups is 3.3431(1), 3.2545(1), and 2.9736(1) Å for Cu2···Cu3, Cu3··· Cu2A, and Cu3···Cu3A, respectively. The angle of Cu−O−Cu is 118.08(2)°, 112.26(5)°, and 97.26(8)° for Cu2−O12−Cu3, Cu3−O12−Cu2A, and Cu3−O12−Cu3A, respectively. Cu2 and Cu3 ions are interlinked by L14− ligands to generate the 2D layers (Figure 5a,c), which are further connected by Cu1 ions to generate a 3D wavelike framework with 1D channels (Figure 5b,d, and Figure S2, Supporting Information), where uncoordinated water molecules occupy. The solvent-accessible volume is estimated to be 32.5% by PLATON. Additionally, the CuII4 cluster and CuII1 are linked through L14− ligands to construct a 3D polyhedral architecture along the c axis (Figure S1, Supporting Information). To better understand the 3D framework, topological analysis is necessary. Regarding the structural features of 2, the [Cu4(μ3OH)2]6+ SBU can be regarded as 6-connected nodes, and the L1 ligand can be reduced to 4-connected nodes (Figure 6a). Thus, complex 2 can be classified as (4,6)-connected net with a Schläfli symbol of (43.63)2(46.66.83) (Figure 6b). Crystal Structure of {[Cd2(L1)(4,4′-bipy)2(H2O)3]·2H2O}n (3). Complex 3 crystallizes in the monoclinic system with space group P21/n and exhibits a 2D → 3D 2-fold interpenetrating framework. The asymmetric unit contains two independent CdII ions, one L1 ligand, two 4,4′-bipy ligands, three coordinated water molecules, and two lattice water molecules.

Figure 3. Topological view of the 3D 4-connected framework with (4.63.82) topology in 1.

Figure 4. Coordination environment of 2 with 30% ellipsoid probability. Symmetry codes: A, 1 − x, − y, 2 − z; B, 1 − x, 1 − y, 1 − z; C, 1 + x, y, z; D, 1 − x, 1 − y, −z.

three carboxyl oxygen atoms from three different L1 ligands, one μ2-oxygen atom [Cu2−O11W = 1.959(8) Å], and one μ3hydroxyl oxygen atom [Cu2−O12 = 1.928(5) Å] (τ = 0.45 for Cu2), indicating that the geometry of Cu2 ion is nearly in D

DOI: 10.1021/acs.cgd.5b00205 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 5. (a) View of the 2D wavelike layers builded by L14− ligands, Cu2, and Cu3 ions along the ab plane. (b) View of the 3D wavelike frameworks formed by Cu1 ions and the 2D layers. (c) View of the 2D structure with 1D channels. (d) View of the 3D architecture.

Figure 6. (a). The 6-connected metal clusters nodes and the 4-connected ligand nodes. (b) The (4,6)-connected topology in 2.

Cd1 ion is seven-coordinated in a distorted pentagonal bipyramid geometry by four oxygen atoms of two L14− ligands, one water molecule, and two nitrogen atoms of two 4,4′-bipy ligands. The distorted axial positions are occupied by N4B and OW12 atoms [(Cd1−N4B = 2.420(3) Å and Cd1−OW12 = 2.352(3) Å], and the angle of N4B−Cd1−OW12 is 174.27(1)° (Figure 7a). Cd2 ion is similar to that of Cd1 ion, four carboxyl O atoms (O6C, O7C, O8, and O9), and one N atom (N3) of the 4,4′-bipy ligand comprise the equatorial plane, while the distorted axial positions are occupied by OW10 and OW11 atoms [(Cd2−OW10 = 2.351(3) Å and Cd2−OW11 = 2.331(4)Å], and the angle of OW10−Cd2−OW11 is 166.00(1)° (Figure 7). Here, the four carboxylate groups of the L 1 ligand chelate the metal ions in a μ 4 η1:η1:η 1:η 1:η 1:η 1:η1 :η1 coordination mode (Scheme S1c, Supporting Information), resulting in a 1D double ladder-like

Figure 7. Coordination environment of 3 with 30% ellipsoid probability (hydrogen atoms and water molecules are omitted for clarity). Symmetry codes: A, x, −1 + y, z; B, −x, 0.5 + y, 0.5 − z; C, −x, −0.5 + y, 1.5 − z.

E

DOI: 10.1021/acs.cgd.5b00205 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 8. (a) View of 1D network. (b) Perspective view of the 3D supramolecular architecture constructed via intermolecular hydrogen bonds, which are shown as a scarlet dash line. (c) Schematic representation of 2D → 2D 2-fold interpenetrating framework. (d) View of 1D grid-like structure constructed by L14− ligands and CdII ions. (e) View of the simplified 2-fold interpenetrating architecture.

structure (Figure 8a,d), which is pillared by one kind of 4,4′bipy ligand to generate an infinite 2D network; the other one displayed a different coordinated mode, including N1 and N2 atoms. N1 atom is coordinated to Cd1 ion, but the N2 atom only provided a hydrogen bond acceptor (O−H···N). To avoid a very large vacant space, the 2D grid layer interweaved to form 2-fold interpenetrating structures (Figure 8c,e), which were further extended into a 3D supermolecular framework by O− H···N hydrogen bonds (Figure 8b). In addition, the guest water molecules occupied the cavities of the network and interacted with the framework via intramolecular hydrogen bonds, which further stabilized the 3D supramolecular framework (Figure S3, Supporting Information). Topologically, both Cd1 and Cd2 ions are considered as 3connected nodes, and each L1 ligand is considered as fourconnected nodes (Figure 9a). Hence, the topology of 3 can be demonstrated as a (3,3,4)-connected net with a Schläfli symbol of (6.82)2(63.83) (Figure 9b), which represents a new topology analyzed by the Topos4.0 program. Crystal Structure of [Zn2(L1)(4,4′-bipy)(H2O)3]n (4). Complex 4 crystallizes in the monoclinic system with space group P21/n. As shown in Figure 10a, the asymmetric unit contains two crystallographically independent ZnII ions, one L1 ligand, one 4,4′-bipy, and three coordinated water molecules. Zn1 ion is five-coordinated to three oxygen atoms from L1 ligands, one N atom from one 4,4′-bipy, and one water molecule [Zn−O, 1.976(2)−2.134(2) Å; Zn−N = 2.047(3) Å] (τ = 0.45 for Zn1), indicating that the geometry of Zn1 ion can be regarded as an intermediate between square pyramid and trigonal bipyramid. Additionally, the four carboxylate groups bridge two

Figure 9. (a) View of 4-connected ligand node and 3-connected metal node. (b) Schematic exhibition of a (3,3,4)-connecting net with (6.82)2(63.83) topology in 3.

ZnII ions to form a dinuclear {Zn2(COO)4} unit (Figure 12a). Zn2 ion is six-coordinated in a distorted octahedral geometry by three carboxylate O atoms from different L1 ligands, one N atom from 4,4′-bipy, and two water molecules [Zn−O, 2.076(3)−2.225(4) Å; Zn−N = 2.132(3) Å] (Figure 10). Then, L14− ligands coordinates to ZnII ions in a μ5η1:η0:η1:η1:η1:η0:η1:η1 coordination mode (Scheme S1d, Supporting Information), resulting in a 2D grid-like structure (Figure 11b), adjacent networks are packed parallel to each other (Figure 11d), which is further extended and stabilized by 4,4′-bipy ligands to form a corrugated 3D architecture (Figure 11a,c), where the 2D parallel arranged networks are embed in. F

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atoms (O7 and O8C) of two L14− ligands, three O atoms (O20W, O21W, and O22W) of three water molecules, and one N atom (N5) of 4,4′-bipy ligand (Figure 13a). The type B contains two L1 ligands, two 4,4′-bipy ligands, three NiII ions, four coordinated water molecules, and two lattice water molecules. Ni3 ion locates at the crystallographic inversion center and is six-coordinated by two carboxylate oxygen atoms (Ni3−O11 = Ni2−O11D = 2.035(3) Å) from three L14− ligands and four coordinated water molecules (Ni3−O23 = Ni3−O23WD = 2.079(4) Å and Ni3−O24 = Ni3−O24WD = 2.062(4) Å) to form a regular octahedral NiO6 coordination geometry. While Ni4 ion is six-coordinated in distorted octahedral NiN2O4 coordination geometry by three atoms (O15E, O16E, and O17) from two L14− ligands, one atom (O25W) from one water molecule, and two nitrogen atoms (N1F and N3) from two 4,4′-bipy ligands (Figure 13b). The other Ni−O and Ni−N distances are in the range of 2.027(3)− 2.156(3) Å and 2.107(5)−2.114(3) Å, respectively (Table S1, Supporting Information). In the type A, six NiII ions (4Ni1 + 2Ni2) are connected by four L14− ligands to give a [Ni6(L1)4] rhombus motif in a μ4η1:η1:η1:η0:η1:η0:η1:η0 coordination mode (Scheme S1e, Supporting Information), which is further interconnected by L14− ligands and Ni2 ions to generate 1D ladder-like chain (Figure S4a,b, Supporting Information). The neighboring 1D chains are then joined by 4,4′-bipy ligands and Ni1 ions to generate 2D pillar-layered framework (Figure 14c), involving 2D (4,4) net (Figure S5a, Supporting Information), where the Ni1···Ni1 distances spanned by 4,4′-bipy ligands and L14− ligands are 11.3386(1) and 10.0879(1) Å, respectively. Similarly to complex 3, the 2D bilayer involves two kinds of 4,4′-bipy ligands; one plays a key role in varying from 1D to 2D, and the

Figure 10. Coordination environment of 4 with 30% ellipsoid probability. Symmetry codes: A, 1 − x, 1 − y, − z ; B, −1 + x, y, −1 + z ; C, −0.5 + x, 1.5 − y, 0.5 + z; D, −0.5 + x, 1.5 − y, −0.5 + z.

If L1 ligand, dinuclear ZnII unit, and each Zn2 ion are considered as 4-connected nodes, 6-connected nodes, and 3connected nodes, respectively (Figure 12a). Thus, the 3D structure of 4 can act as a trinodal (3,4,6)-connected net with a Schläfli symbol of (4.64.8)2(62.8)2(42.66.86.10) (Figure 12b). Crystal Structure of {[Ni7(L1)4(4,4′-bipy)6(H2O)12]·2H2O}n (5). Complex 5 features a (2D → 3D) inclined polycatenation framework with two independent fragments, which exhibit the same topologies (Figure 13a: type A and Figure 13b: type B). Complex 5 crystallizes in the triclinic system with space group P1̅. The type A includes two L1 ligands, four 4,4′-bipy ligands, four NiII ions, and eight coordinated water molecules. Ni1 ion is six-coordinated by three O atoms (O2, O3A, and O4A) of two L1 ligands, one O atom (O19W) of one water molecule, and two N atoms (N2 and N4B) of two 4,4′-bipy ligands in a distorted octahedral geometry. Ni2 ion adopts the same geometry as that of Ni1 ion, which is composed of two O

Figure 11. (a) View of 3D framework built by 2D layers and 4,4′-bipy ligands. (b) View of 2D grid-like structure constructed by L14− ligands and ZnII ions. (c) View of the simplified 3D architecture. (d) View of 2D parallel arranged networks of complex 4. G

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Figure 12. (a) View of 4-connected ligand nodes, 3-connected metal nodes, and 6-connected metal cluster nodes. (d) Schematic representations of the (3,4,6)-connected framework with (4.64.8)2(62.8)2(42.66.86.10) topology in 4.

Figure 13. (a) and (b) Coordination environments of 5 with 30% ellipsoid probability. Symmetry codes: A, 1 + x, y, z; B, x, −1 + y, z; C, 1 − x, − y, 1 − z; D, 2 − x, −y, −z; E, −1 + x, y, z; F, x, 1 + y, z.

The asymmetric unit contains one and a half independent NiII ions, one partially deprotonated L2 ligand, one and a half 4,4′bipy molecules, four aqua ligands, and one lattice water molecule. Ni1 and Ni2 ions exhibit same coordinated geometries. Six-coordinated Ni1 ion displays a distorted octahedral NiN2O4 coordination geometry with three water molecules, one atom of L22− ligand, and two N atoms of two 4,4′-bipy ligands. Similarly to Ni3 ion of complex 5, Ni2 ion also locates at the crystallographic inversion center and is sixcoordinated by two oxygen atoms [Ni2−O8 = Ni2−O8A = 2.0320(2) Å] of two L22− ligands, two water molecules [Ni2− O13W = Ni2−O13WA = 2.087(2) Å], and two N atoms [Ni2−N3 = Ni2−N3A = 2.086(2) Å] of two 4,4′-bipy ligands (Figure 16). The distances of Ni−O and Ni−N bonds span the range of 2.0320(2)−2.087(2) and 2.086(2)−2.124(2) Å, respectively (Table S1, Supporting Information). There are two kinds of 4,4′-bipy ligands in 6; one linked Ni2 ions only to generate a 1D linear chain (Figure 17d), and the other binded Ni1 ions merely to form 1D linear chain, which is further extended by L22− ligands into a 2D backbone along the b axis (Figure 17c). However, it is worth noting that the two kinds of 1D chains interlace with each other similar to skew lines during constructing the 3D structure (Figure 17a). As shown in Figure 17b, the 1D linear chains binded Ni2 ions pass through 2D arciform sheets with the help of L22− ligands to construct a 3D framework along the c axis. To some extent, the 3D network is also reinforced by hydrogen bonds of water molecules and

other has no contributions to control the dimensionality similar to coordinated water molecules and highlighted in navy-blue (Figure 14e). In the type B, four NiII ions (2Ni3 + 2Ni4) are linked by four 3− L1 ligands to give a [Ni4(L1)4] rhombus motif in a μ3η1:η1:η1:η0:η1:η0 coordination mode (Scheme S1f, Supporting Information), which is further interconnected by L13− ligands and Ni3 ions to afford a 1D ladder-like chain (Figure S4c,d, Supporting Information), the 2D pillar-layered framework similar to that of the type A is formed (Figure 14d,f), including 2D (4,4) net (Figure S5b, Supporting Information). It is interesting to note that the 2D layers are interlocked in a parallel fashion with the two nearest neighboring ones to form a fascinating 3D architecture that is 2D → 3D interpenetration and polycatenation framework (Figure 14a,b), possessing identical topologies, which is very unusual to date. From the topological view, both Ni1 and Ni4 ions are considered as 4-connected nodes, and the L1 ligand acts as 3connected nodes (Figure 15a). Therefore, complex 5 can be classified as (3,4)-connected net with a Schläfli symbol of (63)(65.8) (Figure 15b), representing a new topological prototype. Crystal Structure of {[Ni1.5(L2)(4,4′-bipy)1.5(H2O)4]·H2O}n (6). Compared with L1, L2 ligand, which adopts a μ2η1:η0:η1:η0 coordination mode, acts as the role of dicarboxylate acid (Scheme S1g, Supporting Information). Complex 6 crystallizes in the monoclinic system with space group C2/c. H

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Figure 14. (a, b) View of 2D → 3D parallel interpenetration architecture. (c, e) View of the 2D pillar-layered frameworks constructed by 4,4′-bipy and Ni1 ions (color scheme: navy-blue, 4,4′-bipy). (d, f) View of the 2D pillar-layered frameworks constructed by 4,4′-bipy and Ni4 ions.

Figure 16. Coordination environment of 6 with 30% ellipsoid probability (hydrogen atoms and water molecules are omitted for clarity). Symmetry code: A, 1.5 − x, 0.5 + y, 0.5 − z.

Figure 15. (a) View of 4-connected metal nodes and 3-connected ligand nodes. (b) View of (3,4)-connected polycatenation framework with a Schläfli symbol of (63)(65.8) in 5.

(Figure 18a). Therefore, the 3D framework of 6 is a (3,4)connected net with a Schläfli symbol of (4 × 102)2(42.103.12), which represents a new (3,4)-connected topology (Figure 18b). Crystal Structure of {[Ni9(L2)6(dib)12(H2O)18]·18H2O}n (7). Complex 7 crystallizes in the triclinic with space group P1̅ and shows a 3D fascinating architecture. There are nine NiII ions, six L2 ligands that adopt μ2-η1:η0:η1:η0 coordination mode

uncoordinated carboxylate oxygen atoms. The parameters of the hydrogen bonds are listed in Table S2 (Supporting Information). From a topological view, each 2-connected bridging L2 ligand can be regarded as a linear linker. Ni1 and Ni2 ions can be treated as 3-connected and 4-connected nodes, respectively I

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Figure 17. (a) and (b) View of the 3D framework along the b and c axes, respectively. (c) View of 2D backbone along the b axis. (d) View of 1D linear chain formed by 4,4′-bipy and Ni2 ions.

Figure 18. (a) The 3-connected metal nodes, 4-connected metal nodes, and 2-connected L2 nodes. (b) Topological view of (3,4)-connected net with a Schläfli symbol of (4 × 102)2(42.103.12) in 6 (blue spheres: NiII ions).

(Scheme S1h), 12 dib ligands, 18 coordinated water molecules, and 18 lattice water molecules in the asymmetric unit. Ni1, Ni3, and Ni5 ions are six-coordinated in a distorted octahedral geometry by one carboxylate oxygen atom, two oxygen atoms of water molecules, and three nitrogen atoms of three dib

ligands. Ni2 and Ni4 ions are bonded with two oxygen atoms of two L22− ligands, two oxygen atoms of water molecules, and two nitrogen atoms of two dib ligands. Similarly to complex 6, the Ni2 ion locates at the crystallographic inversion center to form a regular octahedral NiN2O4 coordination geometry J

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(Figure 19). The Ni−O and Ni−N distances are in the ranges of 2.061(4)−2.154(4) and 2.057(4)−2.081(4) Å, respectively

with a Schläfli symbol of (63.83)2(85.10) (Figure 21a), never documented to date.

Figure 19. Coordination environment of 7 with 30% ellipsoid probability. Symmetry code: A, 1 − x, 1 − y, 2 − z.

Figure 21. Topological view of a (4,4)-connected net with a Schläfli symbol of (63.83)2(85.10).

(Table S1, Supporting Information). Ni2 and Ni4 ions are bridged by one kind of dib ligands to form 1D chains (Figure 20d), while Ni1, Ni3, and Ni5 ions are linked by another to construct a 2D hexagonal network, which contains six Ni ions (2Ni1 + 2Ni3 + 2Ni5) as well as six dib ligands (Figure 20c). In addition, the adjacent 2D network and 1D chain are interlinked by L22− ligands to build a 3D wavelike framework (Figure 20b). Meanwhile, the 2D network are threaded by the 1D chain with the help of L22− ligands, generating a 3D fascinating network along the a axis (Figure 20a). From the viewpoint of structural topology, if Ni1, Ni3, Ni5, Ni2, and Ni4 ions are wholly simplified as 4-connected nodes, each 2-connected bridging L2 ligand can be regarded as a linker, and then complex 7 can be symbolized as a (4,4)-connected net

Comparing the structures and the synthetic conditions of the seven complexes, the ligands play a key role in determining the final structures under identical solvent and temperature, and the second factor may be metal ions, followed by auxiliary ligands. The coordination modes of L1 ligand are different from L2 completely, owing to the effects of carboxylate positions, and the L2 ligand, which can be a linear linker, adopts μ2-η1:η0:η1:η0 coordination mode in 6 and 7. Complex 1 shows a chiral 3D structure, and 2 exhibits a porous architecture. Obviously, metal ions lead to the structural difference of 1 and 2. The same reaction mixtures (L1 and 4,4′-bipy ligands) were subjected to different synthetic routes by varying metal ions to form diverse architectures in 3, 4, and 5. Complexes 6 and 7 imply the influence of the secondary ligands on the resulting frameworks.

Figure 20. (a) View of the 3D network along the a axis. (b) View of the 3D wavelike framework constructed by the 2D network and 1D chain. (c) View of the 2D hexagonal network constructed by Ni1, Ni3, Ni5 ions, and dib ligands. (d) View of 1D chain constructed by Ni2, Ni4 ions, and dib ligands. K

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− (4J12 + J22 + 4J32 − 2J1J2 − 4J1J3 − 2J2J3)1/2)/kT) + exp((−J1 − J2 − J3 + (4J12 + J22 + 4J32 − 2J1J2 − 4J1J3 − 2J2J3)1/2)/kT)]. Then the CuII5(CuII4 + CuII1) expression of the magnetic susceptibility is

Magnetic Properties. The magnetic susceptibility of 2 was measured from 2 to 300 K. The χM value is 0.00725 cm3 mol−1 at 300 K and slowly increases to a maximum value of 0.59885 cm3 mol−1 at 2 K (Figure S7, Supporting Information). Figure 22 illustrates that the χMT values is 2.15 cm3 K mol−1 at 300 K

χM = χCu4 + χCu1 = (2Ng 2β 2 /kT )[A /B] + Ng 2β 2 /4kT

The best fits have been acquired with g = 2.090(2), J1 = +33.4(1) cm−1, J2 = −21.8(2) cm−1, J3 = +13.0(8) cm−1, R = 3.86 × 10−5 (R = Σ[(χMT)obsd − (χMT)calcd]2/Σ[(χMT)obsd]2). Interestingly, ferromagnetic interactions are predicted in the reported complexes when the angles of dihydroxo-bridged CuII are less than 98.0°;26 however, antiferromagnetic interactions with J2 values of −21.8(2) cm−1 are observed when the angles of Cu3−O−Cu3A (dihydroxo bridge) are 97.3° in 2.27 On the other hand, antiferromagnetic interactions should be produced when the angle of Cu−O−Cu (alkoxo and one hydroxo bridge) is larger than 98.0°, but the angles of Cu2−O−Cu3A and Cu2−O−Cu3 are 112.26(5)° and 118.08(2)°, respectively, showing ferromagnetic interactions with J1 values of +33.4 cm−1 and J3 = +13.0 cm−1. It is worth noting that ferromagnetic interactions dominate mainly via hydroxo and alkoxo bridging modes in a competitive environment. In the discrete CuII4 cluster, ferromagnetic behavior with respect to J2 < 0 is rarely documented to date and different from the tetranuclear clusters reported.28 For 5, the value of χMT is 8.16 cm3 K mol−1 at 300 K in Figure S8, which is greater than the spin-only value of two uncoupled NiII ions (2.0 cm3 K mol−1, S = 1, g = 2.0) (Supporting Information). At 45 K, the value of χMT reaches a maximum of 8.36 cm3 K mol−1 and then drops abruptly to 5.23 cm3 K mol−1 at 2 K, which stands for ferromagnetic coupling between NiII ions (Figure S4b, Supporting Information). Under 45 K, the χMT product decreases quickly owing to zero-field splitting of NiII ions and the spin-polarization mechanism. The data between 2 and 300 K are fitted by the Curie−Weiss law and affords C = 8.17 cm3 K mol−1, θ = 0.49 K; the small and positive value of θ illustrates that the ferromagnetic coupling is very weak. Luminescent Properties. The photoluminescence properties of complexes 1, 3, and 4, together with L1 ligand, were studied in the solid state at room temperature. As shown in Figure 23, intense bands were observed at ca. 353 and 438 nm (λex = 310 nm) for 1, 435 nm (λex = 320 nm) for 3, and 450 nm (λex = 317 nm) for 4, respectively. The fluorescence intensities of 3 and 4 are stronger than 1, owing to the contribution of N-

Figure 22. Plots of χMT vs T and 1/χM vs T (inset) for complex 2. The red line represents the best fits.

per CuII5 (CuII4 + CuII1) unit, which is higher than expected for five uncoupled CuII ions (1.875 cm3 K mol−1, S = 1/2, g = 2.0). At 39 K, the χMT value reaches a maximum of 2.39 cm3 K mol−1 and then drops sharply to 1.18 cm3 K mol−1 at 2 K, which indicates ferromagnetic interactions between the copper ions as well as zero-field splitting. The magnetic susceptibility data can be well fitted to the Curie−Weiss law with a Weiss constant θ = 2.7(7) K, a Curie constant C = 2.17 cm3 K mol−1 in 2−300 K (Figure 22 inset), which shows ferromagnetic coupling. The magnetic interactions in complex 2 can be closely related to its structure (CuII4 + CuII1), while the magnetic exchange of CuII4 and CuII1 should be omitted owing to the distance of CuII4···CuII1 over 5.2243(2) Å (Figure S1, Supporting Information). The chair-shaped tetranuclear clusters provide four different magnetic exchange pathways, which are active and very different: J1 (dialkoxo and one hydroxo bridge), J2 (dihydroxo bridge), J3 (one alkoxo and one hydroxo bridge) (Figure S6, Supporting Information), which can lead to either ferro- or antiferromagnetic coupling. Since the distance of Cu2···Cu2A is 5.890 Å, the value of J4 can be negligible. Thus, the Hamiltonian can be performed using the following expression:25 H = −2J1(SCu2SCu3A + SCu3SCu2A ) − 2J2 SCu3SCu3A − 2J3(SCu2SCu3 + SCu2ASCu3A)

The CuII4 expression of the magnetic susceptibility can be performed: χCu4 = (2Ng 2β 2 /kT )[A /B]

where A = [5 exp((J1 + J3)/kT) + exp((−J1 − J3)/kT) + exp((− J2 − (J12 + J22 + J32 − 2J1J3)1/2)/kT) + exp((−J2 + (J12 + J22 + J32 − 2J1J3)1/2)/kT)] and B = [5 exp((J1 + J2)/kT) + 3 exp((−J1 − J2)/kT) + 3 exp((−J2 − (J12 + J22 + J32 − J1J2)1/2)/kT) + 3 exp((−J2 + (J12 + J22 + J32 − J1J2)1/2)/kT) + exp((−J1 − J2 − J3

Figure 23. Fluorescent emission spectra of complexes 1, 3, and 4 in the solid state at room temperature. L

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CONCLUSION Seven new coordination polymers, which possess diverse structural topologies, have been synthesized solvothermally under similar conditions. The results illustrate that the tetracarboxylate ligands based on the m-benzenedicarboxylate subunit with variable spacers can adopt the diverse coordination modes to construct fascinating structural features such as chiral and pillar-layered frameworks, porous architecture, polycatenation, and interesting topologies for possible application. In addition, the N-donor ligands also display various coordination modes. There are two kinds of 4,4′-bipy ligands in 3, 5, and 6, which act with significantly different functionality in the assembly process, respectively. In 7, Ni2 and Ni4 ions are bridged by one kind of dib ligand to form 1D chains, while Ni1, Ni3, and Ni5 ions are linked by another to construct a 2D hexagonal network. Additionally, the fluorescence (for 1, 3, and 4) and magnetic characters (for 2 and 5) were investigated to elaborate the relevance of their structural and properties. Moreover, complex 2 (CuII4 + CuII1) displays unusual ferromagnetic behavior with respect to J2 < 0. The work provides a possible pathway to modify the structures of coordination polymers by polycarboxylate ligands and Ndonor ligands for its potential applications.

donor ligands to coordination polymers. Intense emission bands of L1 were exhibited at 374 nm (λex = 335 nm) (Figure S9, Supporting Information), which is assigned to the intraligand π* → π transitions, and the HOMO mainly localizes on π-orbitals of benzene ring, whereas its LUMO is delocalized across the entire molecule. (Figure S10, Supporting Information).29 In 1, the HOMO is localized in two benzene rings of L1 ligand, and the LUMO is delocalized in the mbenzenedicarboxylate moiety of the L1 ligand; the emissions can be mainly ascribed to the intraligand charge transfer (ILCT) due to Cd2+ ions with d10 configuration, and simultaneously the red shift is observed owing to the decrease of the HOMO−LUMO energy gap relative to the free L1 ligand (Figure S10, Supporting Information),30 which can be attributed to the intraligand π* → n or π* → π transitions, whereas the blue shift may be ascribed to the enhancement of the ligand conformational rigidity in the assembly process. In the case of the monomer, the HOMO is located on the L1 ligand, while the LUMO is distributed to the 4,4′-bipy ligand in 3 and 4, respectively, following ligand-to-ligand charge transfer (LLCT) (Figure S10, Supporting Information).31 The HOMO−LUMO energy gaps of 3 and 4 are smaller than L1, which lead to the red shift (61 nm for 3 and 76 nm for 4) compared with the free L1 ligand, indicating that the HOMO− LUMO energy gap decreases to make the red shift larger. Powder X-ray Diffraction and Thermogravimetric Analysis. Powder X-ray diffraction (PXRD) patterns of complexes 1−7 were essentially in accordance with the simulated patterns, indicating the pure samples of complexes 1−7 (Figure S11, Supporting Information). To estimate the stabilities of CPs, thermogravimetric (TG) analysis of complexes 1−7 were carried out under a N2 atmosphere from 25 to 800 °C. TG curves for complexes 1− 7 are shown in Figure S12 (Supporting Information). For 1, the 17.1% weight loss in the range of 25−302 °C may be attributed to the removal of five coordinated water molecules; the second weight loss corresponding to the release of organic ligands occurred at about 454 °C. The final mass remnant of 19.5% is likely consistent with the deposition of CdO (calcd 19.5%). For 2, the weight loss of 16.2% could be the loss of four coordinated molecules and two lattice water molecules from 25 to 189 °C, the weight loss of 43.1% is classified as the decomposition of partly ligands in the range of 189−427 °C, and then the collapse of the network of 2 happened. For 3, the first weight loss of 10% in the range of 25 to 232 °C corresponded to the loss of three coordinated water molecules and two lattice water molecules (calcd 9.3%); furthermore, the weight loss of 32.6% indicated to the release of 4,4′-bipy from 226 to 408 °C (calcd 32.2%). The third weight loss of 48.8% could be ascribed to the decomposition of the coordination framework. For 4, the loss of coordinated water molecules (obsd 9.4%, calcd 8.0%) is observed before 275 °C, and the weight loss of 56.0% corresponded to the decomposition of complex 4. The first weight loss is 11.1% owing to the dissociation of water molecules from 25 to 184 °C, and the decomposition of the organic components possesses 72.4% for 5; the final mass of the residue is 16.4%. For 6, it exhibited a loss of 12.1% between 25 and 227 °C, matching well with the removal of all water molecules (calcd 11.9%), and then the pyrolysis of the framework took place. For 7, all water molecules were gradually removed from room temperature to 218 °C (obsd 11.6%, calcd 11.3%), and then the framework disintegrated.

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ASSOCIATED CONTENT

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AUTHOR INFORMATION

S Supporting Information *

CIF files with crystallographic data, the additional figures, magnetic properties, luminescence spectrum, the results of DFT calculations, the PXRD patterns, and TG curves. This material is available free of charge via the Internet at http:// pubs.acs.org. Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by grants from the Natural Science Foundation of China (Nos. 21461023 and 21361023), Fundamental Research Funds for the Gansu Universities.

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REFERENCES

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Crystal Growth & Design

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DOI: 10.1021/acs.cgd.5b00205 Cryst. Growth Des. XXXX, XXX, XXX−XXX