Syntheses, Structures, and Characteristics of Four New MetalâOrganic

Article pubs.acs.org/crystal

Syntheses, Structures, and Characteristics of Four New Metal−Organic Frameworks Based on Flexible Tetrapyridines and Aromatic Polycarboxylate Acids Jin-Song Hu,† Xiao-Qiang Yao,† Ming-Dao Zhang,† Ling Qin,† Yi-Zhi Li,† Zi-Jian Guo,† He-Gen Zheng,*,† and Zi-Ling Xue*,‡ †

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China ‡ Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996-1600, United States S Supporting Information *

ABSTRACT: Solvothermal reactions of tetrakis(4-pyridyloxymethylene)methane (TPOM) with deprotonated isophthalic acid (1,3-H2bdc), 5-hydroxyisophthalic acid (5-OH-H2bdc), benzene-1,3,5-tricarboxylic acid (H3btc), and benzene-1,2,4,5tetracarboxylic acid (H4btc) in the presence of zinc and cobalt salts produce four new complexes, namely, {[Co2(TPOM)(bdc)2(H2O)2]·(H2O)3}n (1), {[Zn2(TPOM)(5-OH-bdc)2]·(DMF)(H2O)2}n (2), {[Co3(TPOM)(btc)2(H2O)]·(H2O)4}n (3), and {[Zn2(TPOM)(btc)2]n (4). Complexes 1 and 2 possess similar 2-fold interpenetrating three-dimensional (3D) framework with bbf topology, but 1 crystallizes in an achiral space group, and 2 crystallizes in chiral space group and displays ferroelectric behavior. Complex 3 reveals a 3D framework with biunclear Co clusters, which displays weak antiferromagnetic character. In complex 4, only H4btc links Zn(II) to generate a 3D porous framework, with TPOM occupying the void space as countercation and template. In addition, photochemical and ferroelectric properties of these new complexes in the solid state have been studied.

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INTRODUCTION The designed construction of metal−organic frameworks (MOFs) from various molecular building blocks is currently a flourishing research field due to their intriguing aesthetic structures and potential applications in sorption,1 heterogeneous catalysis,2 magnetism,3 photochemical areas, and so on.4 Metal−organic frameworks exhibit diversified structures because of the different selected metal ions, the bridging modes and configurations of organic ligands adopted, and the various reaction conditions,5−7 which render it difficult to predict the construction of molecular architectures. Therefore, it still remains a challenge to explore effective synthetic strategies to generate coordination polymers with expected structures and properties. Recently, various mixed-ligand MOFs have been reported;8 it is well-known that combining different ligands in a complex © 2012 American Chemical Society

offers greater tunability of structural frameworks than using a single ligand. In particular, coordination polymers with flexible mixed-ligands exhibit more complex and unusual structures, as functional groups on the ligands offer variable configurations,9,10 which could freely rotate to meet the requirement of coordination geometries of metal ions in the assembly process. Tetrakis(4-pyridyloxy-methylene) methane (TPOM) is a flexible polypyridyl ligand that was concerned in recent years as a result of their pluridentated and excellent coordinated ability. Up to now, the studies of MOFs with TPOM were still Received: October 13, 2011 Revised: May 20, 2012 Published: May 22, 2012 3426

dx.doi.org/10.1021/cg201362x | Cryst. Growth Des. 2012, 12, 3426−3435

Crystal Growth & Design

Article

by the literature methods.12 IR absorption spectra of the complexes were recorded in the range of 400−4000 cm−1 on a Nicolet (Impact 410) spectrometer with KBr pellets. C, H, and N analyses were carried out with a Perkin-Elmer 240C elemental analyzer. Powder X-ray diffraction (PXRD) measurements were performed on a Bruker D8 Advance X-ray diffractometer using Cu−Kα radiation (0.15418 nm) in which the X-ray tube was operated at 40 kV and 40 mA. Luminescent spectra were recorded with a SHIMAZU VF-320 X-ray fluorescence spectrophotometer at room temperature. The as-synthesized samples were characterized by thermogravimetric analysis (TGA) on a PerkinElmer thermogravimetric analyzer Pyris 1 TGA up to 1023 K using a heating rate of 10 K min−1 under N2 atmosphere. The electric hysteresis loops were recorded on a Ferroelectric Tester PrecisionPremier II made by Radiant Technologies, Inc. Synthesis of {[Co2(TPOM)(bdc)2(H2O)2]·(H2O)3}n (1). A mixture of Co(NO3)2·4H2O (29.1 mg, 0.1 mmol), H2bdc (16.6 mg, 0.1 mmol), and TPOM (22.2 mg, 0.05 mmol) was dissolved in 9 mL DMF/H2O (1/2, v/v). The final mixture was placed in a Parr Teflon-lined stainless vessel and heated at 105 °C for 3 days. Purple block crystals were obtained. Yield of the reaction was ca. 64% based on TPOM. Anal. Calcd for C41H38Co2N4O17: C, 50.42%; H, 3.92%; N, 5.74%. Found: C, 50.57%; H, 3.81%; N, 5.69%. IR (KBr, cm−1): 3405(w), 1649 (s), 1633(s), 1584(s), 1511(s), 1449(m), 1371(s), 1349(s), 1317(s), 1294(s), 1196(s), 1128(s), 1085(m), 996(m), 861(m), 804(m). Synthesis of {[Zn2(TPOM)(5-OH-bdc)2]·(DMF)(H2O)2}n (2). Compound 2 was prepared similar to that of compound 1 by using Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), 5-OH-H2bdc (18.2 mg, 0.1 mmol), and TPOM (22.2 mg, 0.05 mmol) dissolved in 10 mL of DMF/ H2O (1/1, v/v). Colorless block crystals were obtained in 58% yield based on TPOM. Anal. Calcd for C44H41Zn2N5O17: C, 50.69%; H, 3.96%; N, 6.72%. Found: C, 50.48%; H, 4.04%; N, 7.66%. IR (KBr, cm−1): 3408(s), 1616(s), 1566(s), 1511(s), 1438(m), 1401(m), 1352(s), 1303(s), 1317(s), 1033(m), 977(m), 854(w), 825(m), 787(m), 726(m), 542(w). Synthesis of {[Co3(TPOM)(btc)2(H2O)]·(H2O)4}n (3). A mixture of Co(NO3)2·4H2O (29.1 mg, 0.1 mmol), H3btc (21.0 mg, 0.1 mmol), and TPOM (22.2 mg, 0.05 mmol) was dissolved in 10 mL of DMF/H2O (1/4, v/v). The final mixture was placed in a Parr Teflon-lined stainless vessel and heated at 95 °C for 3 days. Purple block crystals were

insufficient.11 Our research interests concern the use of mixedligands to give new architectures and topologies; we thus selected TPOM, 1,3-H2bdc, 5-OH-H2bdc, H3btc, and H4btc as ligands (Scheme 1) with divalent transition salts, and solvothermally Scheme 1. Polycarboxylate Ligands and N-Containing TPOM

synthesized four new coordination polymers {[Co2(TPOM)(bdc)2(H2O)2]·(H2O)3}n (1), {[Zn2(TPOM)(5-OH-bdc)2]· (DMF)(H2O)2}n (2), {[Co3(TPOM)(btc)2(H2O)]·(H2O)4}n (3), and {[Zn2(TPOM)(btc)2]n (4). These new compounds are characterized by elemental analysis, IR spectra, and X-ray crystallography. Crystal structures, topological analyses, and thermal properties of the compounds are presented. In addition, the photoluminescence, magnetic, and ferroelectric properties for complexes are also discussed.

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EXPERIMENTAL SECTION

Materials and Measurements. Reagents and solvents employed were commercially available and used as received. TPOM was prepared

Table 1. Crystallographic Data and Structure Refinement Details for Complexes 1−4

a

complex

1

2

3

4

formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) Z V (Å3) Dcalcd(g cm−3) μ(Mo Ka) (mm−1) F(000) theta min−max (deg) tot., uniq. data R(int) observed data [I > 2σ(I)] R1,wR2a (I > 2σ(I)) S min and max resdens. (e·Å−3)

C41H38O17N4Co2 976.61 monoclinic P2/c 10.4063(12) 9.3137(11) 23.889(3) 90.00 91.603(2) 90.00 2 2314.4(5) 1.427 0.793 1421 0.998, 25.00 11122, 4082 0.0913 3359 0.0573, 0.1599 1.082 −0.357, 0.710

C44H41O17N5Zn2 1042.60 monoclinic P2 10.7263(16) 9.0056(13) 12.9899(19) 90.00 104.047(3) 90.00 1 1217.3(3) 1.273 1.047 476 0.997, 25.00 5798, 3876 0.0314 3315 0.0419, 0.0858 0.962 −0.283, 0.625

C43H38O21N4Co3 1123.50 monoclinic P2(1)/c 9.5307(14) 14.028(2) 36.112(5) 90.00 95.256(3) 90.00 4 4807.7(12) 1.453 1.096 2132 0.993, 25.00 23380, 8420 0.1017 6812 0.0538, 0.1280 1.046 −0.613, 0.885

C45H32O20N4Zn2 1079.53 tetragonal I41/acd 16.1936(9) 16.1936(9) 29.884(3) 90.00 90.00 90.00 8 7836.5(10) 1.809 1.325 4304 1.00, 26.00 22216, 2407 0.0545 1611 0.0419, 0.1105 1.06 −0.392, 0.288

R1 = Σ||Fo| − |Fc||/|Σ|Fo|. wR2 = {Σ[w(Fo2 − Fc2)2]/Σ[w(Fo2)2]}1/2; where w = 1/[σ2(Fo2) + (aP)2 + bP] and P = (Fo2 + 2Fc2)/3. 3427



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obtained. Yield of the reaction was ca. 51% based on TPOM. Anal. Calcd for C43H38Co3N4O21: C, 45.97%; H, 3.41%; N, 4.99%. Found: C, 45.12%; H, 3.55%; N, 5.09%. IR (KBr, cm−1): 3415(w), 1643 (s), 1632(s), 1574(s), 1504(s), 1457(m), 1373(s), 1347(s), 1321(s), 1289(s), 1194(s), 1131(s), 1091(m), 1015(w), 994(m), 946(w), 853(m), 816(m), 804(m), 570(w). Synthesis of {[Zn2(TPOM)(btc)2]}n (4). A mixture of Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), H4btc (25.4 mg, 0.1 mmol), and TPOM (22.2 mg, 0.05 mmol) was dissolved in 9 mL of DMF/H2O (1/2, v/v). The final mixture was heated at 100 °C for 2 days. Colorless block crystals were obtained in 78% yield based on TPOM. Anal. Calcd for C45H32Zn2N4O20: C, 50.07%; H, 2.99%; N, 5.19%. Found: C, 49.98%; H, 3.14%; N 5.16%. IR (KBr, cm−1): 3397(w), 3070 (w), 1624(s), 1575(s), 1504(s), 1457(m), 1373(s), 1321(s), 1291(s), 1194(s), 1131(m), 1091(m), 1015(m), 995(w), 946(w), 922(m), 854(w), 816(m), 805(m), 716(w), 666(w), 634(w), 608(w), 522(w). X-ray Crystallography. Single crystals of 1−4 were prepared by the methods described in the synthetic procedure. X-ray crystallographic data of 1−4 were collected at room temperature using epoxy-coated crystals mounted on glass fiber. All measurements were made on a Bruker Apex Smart CCD diffractometer with graphite-monochromated Mo−Kα radiation (λ = 0.71073 Å). The structures of complexes 1−4 were solved by direct methods, and the non-hydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using a full-matrix least-squares procedure based on F2 values.13 The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent atoms. The distribution of peaks in the channels of 2 and 3 were chemically featureless to refine using conventional discrete-atom models. To resolve these issues, the contribution of the electron density by the remaining solvents was removed by the SQUEEZE routine in PLATON.14 The numbers of solvent molecules were obtained by element analyses and TGA. The relevant crystallographic data are presented in Table 1, while the selected bond lengths and angles are given in the Supporting Information (Table S1).

Crystal Structure of {[Zn2(TPOM)(5-OH-bdc)2]·(DMF)(H2O)2}n (2). Compound 2 crystallizes in the chiral space group P2, and the Flack’s parameter is 0.064(15). As shown in Figure 2a, two types of Zn(II) ions are all four-coordinated and reside in the distorted tetrahedral coordination environment defined by two oxygen atoms from two different 5-OH-bdc2− anions and two nitrogen atoms from two TPOM ligands. The bond lengths of Zn−O and Zn−N are 1.930−1.945 Å and 2.036−2.065 Å. In compound 2, TPOM ligand adopts a comformation holding the four pyridyl groups in irregular orientations, the N···Ccore···N angles range from 75.136 to 127.932°. The −CH2O− spacers that connect each pyridyl group to the core adopt conformation that is more extended than 1 with Ccore−CH2−O−C torsion angles of 170.307° and 178.557°. As a result of the chiral space group, there exists a 1D left-handed helical channel constructed by Zn(II) and 5-OH-bdc2− (Figure 2b). Each tetrahedral Zn atom coordinates to TPOM ligands to form an infinitely wave-like 2D network along the a axis (Figure 2c). The 5-OH-bdc2− anions link two Zn atoms belonging to different 2D networks to form a 3D framework (Figure 2d). In order to minimize the cavities and to stabilize the framework during the assembly process, another identical network across the cavities gives a 2-fold interpenetrating three-dimensional architecture (Figure 2e). By analysis, the whole structure is also represented as a bbf network topology. Crystal Structure of {[Co3(TPOM)(btc)2(H2O)]·(H2O)4}n (3). Compound 3 crystallizes in the space group P21/c. The asymmetric unit contains three Co(II) (Co1, Co2, and Co3) cations, one TPOM molecule, two btc3− anions, and one coordinated water. As shown in Figure 3a, carboxylate groups of btc3− adopt three different coordination modes: one is chelating in a bidentate mode, another is bridging bidentate, and the third is monodentate bridging mode. Co1 is in a tetragonal pyramid coordination environment, which is defined by three carboxylic oxygen atoms from three different btc3− anions, one coordinated water, and one coordinated N atom from TPOM. Co2 and Co3 reside in distorted octahedral coordination spheres, Co2 is defined by five oxygen atoms (O8, O10, O11, O13, and O14) from four different btc3− anions and one nitrogen atom (N1) from TPOM ligand, while Co3 is defined by four oxygen atoms from two different btc3− anions (O4, O5, O6, and O7) and two nitrogen atoms (N2 and N3) from two TPOM ligands. The Co−O lengths range from 2.045−2.28 Å and Co−N from 2.082−2.122 Å. The Co1 and Co2 are bridged by carboxylate ligands to form a binuclear cluster unit, and the distance of Co(1)···Co(2) is 3.399 Å. Each Co atom links btc3− anion to form an infinitely 3D network with rectangular channel along the b axis. As shown in Figure 3b, noteworthy of this network is the presence of a pair of left-handed and right-handed 1D helical channels alternately arranged, which are formed by the btc3− linked to Co3 atoms, and the distance of Co···Co is 9.441 Å, while the binuclear Co SBU were linked by btc3− to form 1D ladder chains along c axis. Similarly, the TPOM ligands coordinated to Co3 atoms also formed lefthanded and right-handed 1D helical channels alternately along the b axis, the distance of Co···Co is 14.548 Å (Figure 3c). Furthermore, the hand-directions of two helical channels are same. The TPOM and btc3− are linked to Co atoms to generate a 3D framework (Figure 3d). The binuclear Co cluster can be regarded as 6-connected nodes with all crystallographical independent TPOM ligands and btc3− acting as 4- and 3-connected nodes. Therefore, the whole structure can thus be represented as a {42·64·89}{42·6}{63}{64·82}{65·8} network topology (Figure 3e). Crystal Structure of {[Zn2(TPOM)(btc)2}n (4). Compound 4 was solved in the space group I41/acd. The asymmetric unit

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RESULTS AND DISCUSSION Crystal Structure of {[Co2(TPOM)(bdc)2(H2O)2]·(H2O)3}n (1). Compound 1 crystallizes in the space group of P2/c. As shown in Figure 1a, there are two types of coordination environments around the Co(II) ions. Co1 is four-coordinated and resides in distorted tetrahedral coordination environment defined by two oxygen atoms from two different bdc2− anions and two nitrogen atoms from two TPOM ligands. Co2 is in an octahedral coordination sphere, which is defined by two carboxylic oxygen atoms, two coordinated water O atoms at the equatorial position, and the other two coordinated N atoms from TPOM at the axial position. The bond lengths of Co−O and Co−N are 1.941−2.154 Å and 2.050−2.163 Å. In compound 1, the TPOM ligand adopts a conformation holding the four pyridyl groups in irregular orientations, the N···Ccore···N angles range from 90.306 to 125.995°. The −CH2O− spacers that connect each pyridyl group to the core adopt conformations that are substantially extended with Ccore− CH2−O−C torsion angles of 165.832° and 175.720°. An interesting feature in this network is that a pair of meso-helical channels exist (Figure 1b). Each Co atom coordinates to TPOM to form infinitely a wave-like 2D network along the b axis (Figure 1c). The bdc2− anions link two Co atoms belonging to different 2D networks to form a 3D framework (Figure 1d). The potential voids are large enough to be filled via mutual interpenetration of an independent equivalent framework, generating a 2-fold interpenetrating 3D architecture (Figure 1e). The Co(II) and TPOM can be regarded as 4-connected nodes and the bdc2− anions acting as linker. Compound 1 has a bbf network topology (with the Schläfli symbol {64·82}{66}2) (Figure 1f). 3428



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Figure 1. (a) Coordination environment of the Co(II) ions in 1. The hydrogen atoms are omitted for clarity. Symmetry codes: #1 = 1 − x, y, 1.5 − z; #2 = 1 − x, 1 − y, 1 − z; #3 = 2 − x, 1 − y, 1.5 − z; #4 = 2 − x, 2 + y, 1.5 − z; #5 = x, 2 + y, z. (b) View of 1D meso-helical chain. (c) View of the wave-like 2D sheet by TPOM and Co ions along the b axis. (d) View of 3D framework of 1 along the a axis. (e) View of 2-fold interpenetrating 3D framework of compound 1 along the a axis. (f) Schematic representation of 2-fold interpenetrating 3D framework with bbf topology.

contains half of a Zn(II) cation, half of a btc4− anion, and a quarter of a TPOM lattice molecule. As shown in Figure 4a, carboxylate groups of btc4− all adopt monodentate coordinated

modes, so the Zn (II) has a tetrahedral geometry with four carboxylic O atoms from four btc4− anions. The Zn−O lengths are 1.927−1.967 Å. 3429



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Figure 2. (a) Coordination environment of the Co(II) ion in 2. The hydrogen atoms are omitted for clarity. Symmetry codes: #1 = −x, y, 1 − z; #2 = 1 − x, y, 2 − z; #3 = x, 2 + y, z; #4 = −x, 2 + y, 1 − z; #5 = −x, y, 2 − z. (b) View of 1D left-handed helical chain. (c) View of the wave-like 2D sheet by TPOM and Co anions along the b axis. (d) View of 3D framework of 2 along the a axis with bbf topology. (e) View of 2-fold interpenetrating 3D framework of compound 2 along the a axis.

In compound 4, the completely deprotonated btc4− anions link four Zn atoms through the carboxylate coordination to form a 3D framework with larger open channels. From the c axis, there exist square channels with the size of ∼6.2 × 6.2 Å (Figure 4b), while the TPOM ligand is not coordinated, which occupies the void space as a countercation and arranges in reciprocal

chiasmata mode (Figure 4c). From the TGA curve, there was no departure stage until the framework collapsed, that is to say TPOM plays a critical role, which keeps the framework stable. The btc4− and Zn2+ center can be regarded as four-connected linker and node. By analyzing, compound 4 has a PtS network topology (Figure 4d). Though there are many reports about 3430



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Figure 3. (a) Coordination environment of the Co(II) ion in 3. The hydrogen atoms are omitted for clarity. Symmetry codes: #1 = −1 + x, y, z; #2 = 1 + x, −1 + y, z; #3 = 1 − x, −1 − y, −z; #4 = −1 + x, −1 + y, z; #5 = 1 − x, 0.5 + y, 0.5 − z; #6= −1 − x, −0.5 + y, 0.5 − z. (b) View of 3D framework by btc3− and Co anions along the b axis; left-handed and right-handed 1D helical channel arranged alternately. (c) Left-handed and right-handed 1D helical channels arranged alternately constructed by TPOM and Co ions. (d) View of 3D framework of 3 along the b axis. (e) Schematic representation of 3D {42·64·89}{42·6}{63}{64·82}{65·8} framework of 3.

Thermal Analysis and PXRD Results. To estimate the stability of the coordination architectures, their thermal behaviors were studied by TGA (Supporting Information, Figure S1).

1,2,4,5-H4BTC and Zn forming the Zn(CO2)4 cluster, so far as we know, 4 is the first example of TPOM as a countercation. The symmetry of complex 4 is also the highest in these compounds. 3431



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Figure 4. (a) Coordination environment of the Zn(II) ion in 4. The hydrogen atoms are omitted for clarity. Symmetry codes: #1 = 0.5 − x, 0.5 + y, z; #2 = 0.25 + x, −0.25 + y, 0.25 − z; #3 = 0.75 − x, 0.25 + y, 0.25 − z; #4 = 0.5 − x, y, −z. (b) View of 3D framework by btc4− and Zn. (c) TPOM occupying the void space as countercation and arranging in reciprocal chiasmata mode. (d) Schematic representation of PtS framework.

long course of weight loss (8.09%) from 20 to 230 °C, corresponding to the departure of lattice and coordinated water; the structure was decomposed starting at 407 °C. Complex 4 has no solvents, it was decomposed starting at 348 °C. The PXRD experimental and computer-simulated patterns of the corresponding complexes are shown in the Supporting Information

For complex 1, a weight loss of 11.88% is observed from 20 to 198 °C, corresponding to the departure of the lattice and coordinated water; the structure was then decomposed starting at 410 °C. The TGA curve of 2 is a weight loss of 10.93% from 20 to 260 °C, corresponding to the departure of the lattice water and DMF; the framework collapsed at 380 °C. Compound 3 has a 3432



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Supporting Information (Figure S2). Intense emission of the free 5-OH-H2bdc was observed with wavelength of 350 to 410 nm (λmax = 365 nm). The curve of free TPOM ligand showed an infirm emission with wavelength from 420 to 475 nm (λmax = 450 nm), which could be attributed to the π* → π or π* → n transitions. Complex 2 exhibits an emission character similar to that of the free 5-OH-H2bdc, the maximum emission peak is at 460 nm (λex = 360 nm), and shows a highly red shift compared with that of the 5-OH-H2bdc, which is probably assigned to the chelation of the carboxylate ligands to the central metals.15 Magnetic Properties of Complexes 1 and 3. The magnetic measurements were performed on polycrystalline samples of 1 and 3 using a SQUID magnetometer under an applied field of 2000 Oe over the temperature range 2−300 K, and the results are shown in Figures 5 and 6. The temperature dependence of the magnetic susceptibility of 1 in the form of χMT is displayed in Figure 5. As the temperature cools, χMT continuously decreases from 2.73 cm3 K mol−1 at 300 K to 1.72 cm3 K mol−1 at 1.8 K. The value of χMT at 300 K is greater than the expected value for one isolated high-spin Co(II) ions (g = 2 and S = 3/2), which is caused by an unquenched orbital contribution arising from the 4T1g ground state of Co(II).16 The value of χMT for complex 3 at 300 K is 5.55 cm3 K mol−1. As the temperature cools, χMT continuously decreases to 0.41 cm3 K mol−1 at 1.8 K. The magnetic susceptibilities of 1 and 3 can be fitted well by the Curie−Weiss law χ = C/(T − θ), with θ = −9.76 K, C = 2.84 cm3 mol−1 K for 1, and θ = −8.16K, C = 5.73 cm3 mol−1 K for 3. The negative θ values of both suggest weak antiferromagnetic interaction between Co ions. Ferroelectric Property of Complex 2. Complex 2 crystallizes in a chiral space group (P2), which is associated with the point groups of C2; one of the ten polar point groups (C1, Cm, C2, C2v, C3, C3v, C4, C4v, C6, and C6v) may have the potential to display ferroelectric behavior. The electrical hysteresis loop of complex 2 was recorded under different temperatures by using crystal sample plates.17 At room temperature, the remnant electric polarization (Pr) is 0.052 μC/cm2 and electric coercive field (Ec) is 5.755 kV/cm, respectively; saturation of the spontaneous polarization (Ps) is ca. 0.451 μC/cm2. At 0 °C (blue curve), the remnant electric polarization and electric coercive field are 0.015 μC/cm2 and 0.628 kV/cm, respectively; saturation of the spontaneous polarization is ca. 0.482 μC/cm2. When in liquid nitrogen conditions (red curve), the remnant electric polarization and electric coercive field are 0.045 μC/cm2 and 2.052 kV/cm, and

Figure 5. Temperature dependence of the χMT product for 1 at 2 kOe. Inset: temperature dependence of 1/χM for 1. The red line shows the best-fit curve according to the Curie−Weiss fit law.

Figure 6. Temperature dependence of the χMT product for 3 at 2 kOe. Inset: temperature dependence of 1/χM for 3. The red line shows the best-fit curve according to the Curie−Weiss fit law.

(Figures S3−S6). The results demonstrate that the experimental PXRD patterns perfectly match the simulated patterns based on the single-crystal X-ray data. Photochemical Properties. The luminescent properties of free ligands TPOM and 5-OH-H2bdc, as well as complex 2 in the solid state at room temperature, were studied as depicted in the

Figure 7. Polarization versus applied electric field curve (electric hysteresis loop) of 2 (a) at room temperature, (b) at 0 °C (blue), and in liquid nitrogen conditions (red). 3433



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the spontaneous polarization is ca. 0.682 μC/cm2 (Figure 7). Obviously, the remnant electric polarization and electric coercive field are the least at 0 °C. The Pr and Ec of 2 is comparable with that of the crystal sample of MOF [Zn(1,4-bimb)(D-ca)]n [DH2ca = D-camphoric acid, 1,4-bimb = 1,4-bis(imidazol-1ylmethyl)-benzene] (Pr = 0.052 μC/cm2, Ec = 5.83 kV/cm),17h while smaller than compound [Zn 2 Co(tib) 3 (H 2 O) 5 ][Zn6(tib)2(1,2,4-BTC)6]·12.7H2O [tib = 1,3,5-tris(1-imidazolyl) benzene, 1,2,4-H3BTC = 1,2,4-benzenetricarboxylic acid] (Pr = 0.177 μC/cm2, Ec = 17.68 kV/cm).17i

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CONCLUSIONS In summary, a series of three-dimensional Co(II) and Zn(II) coordination polymers were prepared under solvothermal conditions by using TPOM and rigid polycarboxylate ligands. The results show that TPOM is a good candidate for construction coordination polymers with diverse structures. These compounds not only have intriguing structures but also exhibit interesting properties, which may be a good candidate for photoelectric and magnetic materials. It is anticipated that more and more coordination polymers containing TPOM will be synthesized with novel structures and properties.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format; selected bond lengths and angles and patterns of photochemistry, TGA, and PXRD. This material is available free of charge via the Internet at http://pubs. acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (H.-G.Z.); [email protected]. edu (Z.-L.Z). 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. 20971065, 21021062, and 91022011), National Basic Research Program of China (2010CB923303), and US National Science Foundation (CHE-1012173 to Z.-L.X.).

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