Syntheses, Structures, and Magnetic Properties of Three Novel Metal

China, and College of Chemistry, Inner Mongolia UniVersity for Nationalities, Tongliao 028000,. China. ReceiVed August 5, 2005; ReVised Manuscript ...
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CRYSTAL GROWTH & DESIGN

Syntheses, Structures, and Magnetic Properties of Three Novel Metal-Malate-Bipyridine Coordination Polymers with Layered and Pillared Topology

2006 VOL. 6, NO. 5 1101-1106

Li-Mei Duan,†,‡ Feng-Tong Xie,† Xiao-Yan Chen,§ Yan Chen,† Yu-Kun Lu,† Peng Cheng,§ and Ji-Qing Xu*,† College of Chemistry and State Key Laboratory of Inorganic Synthesis and PreparatiVe Chemistry, Jilin UniVersity, Changchun 130021, China, College of Chemistry, Nankai UniVersity, Tianjin 300071, China, and College of Chemistry, Inner Mongolia UniVersity for Nationalities, Tongliao 028000, China ReceiVed August 5, 2005; ReVised Manuscript ReceiVed February 25, 2006

ABSTRACT: The combination of metal ions with malic acid (hydroxybutane diacid) and 4,4′-bipyridine ligands under hydro(solvo)thermal conditions has resulted in the formation of three novel coordination polymers, {[M(C4H4O5)(bipy)0.5]‚H2O}n (M ) CoII (1), NiII (2), 0.3CoII + 0.7NiII (3); C4H4O52- ) malate dianion, bipy ) 4,4′-bipyridine). The metal ions were interconnected by R- and β-carboxylates of malate to produce infinite [M(C4H4O5)]n layers, which were further pillared by bridging bipy molecules to form a 3D network. The µ3-malate ligand exhibits a pentadentate coordination mode, with all of the five oxygen atoms participating in the coordination. The magnetic pathways of three compounds are through M-O-C-O-M with nonplanar skew-skew conformations; compound 1 shows antiferromagnetic interactions, while 2 is ferromagnetic, due to different electronic configurations of the metal ions. Introduction The design and synthesis of metal-organic frameworks with original architectures, which could offer great potential for chemical and structural diversity, is one of the major current challenges in inorganic chemistry. Enormous effort in this field has been focused on the construction of various extended networks by using neutral donor ligands, organic anions, and their combination. Among organic anions, the di- and polycarboxylates have received considerable attention, due to the wide variety of architectures and topologies as well as great potential applications in many fields. Either rigid aromatic dicarboxylates1-3 or flexible aliphatic dicarboxylates (such as malonate, succinate, fumarate, glutarate, adipate, etc.)4 are capable of binding metal centers in versatile coordination modes, leading to a wide variety of extended structures. Moreover, di- and polycarboxylates are frequently used as magnetic superexchange pathways between the metal ions, due to their versatile carboxylate-bridging coordination modes, which can transmit magnetic coupling interactions to different degrees.5 In comparison with the flexible dicarboxylate ligands, the presence of a hydroxyl group in the hydroxyl polycarboxylates (HPCs), such as malate, citrate, tartrate, etc., provides an additional coordination site and allows the formation of five- and six-membered rings, which can stabilize the solid networks. Just as for aliphatic dicarboxylates, the HPCs could also act as suitable candidates in designing extended magnetic networks, and recently, a few novel metalorganic networks6 based on malate and citrate have been reported which exhibit different magnetic behaviors. Though the HPCs are useful biological reagents with excellent chelating ability, hydrophilic nature, and biological properties, they have been less frequently considered as building blocks to construct the inorganic-organic hybrid networks.6-8 The bond* To whom correspondence should be addressed. Fax: +86-4318499158. E-mail: [email protected]. † Jilin University. ‡ Inner Mongolia University for Nationalities. § Nankai University.

ing characteristics of malic acid (hydroxybutane diacid) with transition-metal ions have been investigated, and some typical coordination modes for malate are summarized in Chart 1 (modes I-VIII), and various modes, such as bidentate9 (mode I), tridentate10(mode II), tetradentate7,11 (modes III-VI), and pentadentate12 (modes VII and VIII), have been presented in the literature. To the best of our knowledge, most of these compounds are monomeric, dimeric, and tetrameric; only a few extended networks containing malate ligands have been reported.6a,7 In all known malate-bridging compounds, the oxygen atoms of the alkoxyl or hydroxyl groups participate in the coordination along with R- and β-carboxylate groups, which allows the formation of five- and six-membered rings, stabilizing the solid networks. Here, we report the syntheses, structures, and magnetic behaviors of the three coordination polymers {[M(C4H4O5)(bipy)0.5]‚H2O}n (M ) CoII (1), NiII (2), 0.3CoII + 0.7NiII (3); C4H4O52- ) malate dianion, bipy ) 4,4′-bipyridine), which possess 3-D network structures with layered and pillared topologies. Experimental Section General Methods. Reagents were purchased commercially and used without further purification. The elemental analyses were conducted on a Perkin-Elmer 2400 elemental analyzer. Inductively coupled plasma (ICP) analyses were performed on a Perkin-Elmer Optima 3300DV spectrometer. Infrared spectra were measured on KBr disks with a Perkin-Elmer spectrometer in the 4000-400 cm-1 region. XPS measurements were performed on single crystals with an ESCALAB MARKII apparatus, using Mg KR X-ray radiation as the excitation source. A NETZSCH STA 449C unit was used to carry out the TGA and DTA analyses in air with a heating rate of 20 °C min-1. Magnetic measurements were obtained using an MPMS-XL magnetometer at H ) 5000 Oe in the temperature range 2-300 K. Synthesis of {[Co(C4H4O5)(bipy)0.5]‚H2O}n (1). Compound 1 was hydro(solvo)thermally synthesized from a mixture of CoAc2‚4H2O (1.0 g, 4 mmol), 4,4′-bipyridine (0.6 g, 3 mmol), and malic acid (0.4 g, 3 mmol) in 20 mL of water and 10 mL of absolute alcohol with a pH about 4.5. After being stirred for 1 h, the mixture was sealed in a Teflonlined steel vessel and heated at 160 °C under autogenous pressure for 3 days. After the mixture was cooled, the dark pink crystalline material

10.1021/cg050382q CCC: $33.50 © 2006 American Chemical Society Published on Web 04/05/2006

1102 Crystal Growth & Design, Vol. 6, No. 5, 2006

Duan et al.

Chart 1. Coordination Modes of Malate Anions

Table 1. Crystallographic Data and Structure Refinement Details for of 1-3

formula fw T (K) cryst syst space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z Dc (g cm-3) µ (mm-1) GOF on F2 R1a (I > 2σ(I)) wR2b a

1

2

3

C9H10CoNO6 287.11 293(2) orthorhombic Pbcn 9.3582(19) 10.953(2) 24.370(5)

C9H10NNiO6 286.89 293(2) monoclinic P21/c 13.104(3) 9.3549(19) 10.883(2) 113.08(3) 1227.3(4) 4 1.553 1.595 1.053 0.0631 0.2261

C9H10Co0.3NNi0.7O6 286.96 293(2) orthorhombic Pbcn 9.3525(19) 10.917(2) 24.175(5)

2497.9(9) 8 1.527 1.388 0.994 0.0454 0.1396

2468.3(9) 8 1.552 1.532 1.039 0.0566 0.1587

R1 ) ∑||Fo| - |Fc||/∑|Fo|. b wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]}1/2.

was separated, washed with distilled water, and air-dried (ca. 50% yield, based on cobalt). Anal. Calcd for C9H10CoNO6: Co, 20.53; C, 37.65; H, 3.51; N, 4.88. Found: Co, 19.82; C, 37.46; H, 3.66; N, 4.75. Main IR features (KBr disk, ν/cm-1): 3440 (s), 2934 (m), 1609 (s), 1574 (s), 1423 (s), 1391 (m), 1301 (m), 1227 (m), 1084 (m), 839 (w). Synthesis of {[Ni(C4H4O5)(bipy)0.5]‚H2O}n (2). Compound 2 was prepared from a mixture of NiAc2‚4H2O (1.0 g, 4 mmol), 4,4′-bipyridine (0.6 g, 3 mmol), and malic acid (0.4 g, 3 mmol) in 30 mL of water/ alcohol solution. Then, by the same procedure as for 1, green crystals were obtained (ca. 65% yield, based on nickel). Anal. Calcd for C9H10NNiO6: Ni, 20.46; C, 37.68; H, 3.51; N, 4.88. Found: Ni, 20.75; C, 37.81; H, 3.70; N, 4.79. Main IR features (KBr disk, ν/cm-1): 3440 (s), 2921 (m), 1610 (s), 1575 (s), 1422(m), 1388 (m), 1307 (m), 1228 (w), 1082 (m), 840 (w). Synthesis of {[M(C4H4O5)(bipy)0.5]‚H2O}n (3; M ) 0.3CoII + 0.7NiII). The purplish red crystals of compound 3 were prepared by following the procedure detailed above for 1 but using CoAc2‚4H2O (0.5 g, 2 mmol) and NiAc2‚4H2O (0.5 g, 2 mmol) instead of the previous cobalt salt (ca. 70% yield, based on nickel). Anal. Calcd for C9H10Co0.3NNi0.7O6: Co, 6.16; Ni, 14.32; C, 37.68; H, 3.51; N, 4.88. Found: Co, 6.35; Ni, 14.17; C, 37.54; H, 3.42; N, 4.70. Main IR features (KBr disk, ν/cm-1): 3441 (s), 2929 (m), 1610 (s), 1578 (s), 1422 (m), 1388 (m), 1303 (m), 1228 (w), 1083 (m), 840 (w). X-ray Crystallography. All measurements were made on a Rigaku RAXIS-RAPID diffractometer, and the data collections were performed at 293(2) K by using graphite-monochromated Mo KR radiation (λ ) 0.710 73 Å). The structures were solved by direct methods and refined with full-matrix least-squares techniques using SHELXS-97 and SHELXL-97 programs, respectively. Non-hydrogen atoms were refined anisotropically, and the hydrogen atoms were positioned with idealized geometries. Compounds 1-3 possess similar structures but belong to different space groups. Further details of the X-ray structural analysis are given in Table 1. Selected bond lengths and angles for compounds 1-3 are given in Table 2.

Table 2. Selected Bond Lengths (Å) and Angles (deg) for Compounds 1-3 1a

2b

3c

M-O(2) M-O(1) M-N(1) M-O(5) M-O(4) M-O(3) O(1)-C(1) O(2)-C(1)#1 O(3)-C(2) O(4)-C(4) O(5)-C(4)#2 N(1)-C(9) N(1)-C(5)

2.031(2) 2.067(2) 2.099(3) 2.106(2) 2.133(2) 2.163(2) 1.253(4) 1.249(4) 1.432(4) 1.280(3) 1.250(4) 1.329(4) 1.336(4)

2.029(4) 2.042(4) 2.042(4) 2.066(4) 2.095(4) 2.109(4) 1.256(7) 1.250(6) 1.442(6) 1.268(6) 1.260(6) 1.338(8) 1.325(8)

2.018(3) 2.064(3) 2.068(3) 2.074(3) 2.110(3) 2.118(3) 1.251(5) 1.254(5) 1.448(5) 1.269(5) 1.254(5) 1.322(6) 1.340(6)

O(2)-M-O(1) O(2)-M-N(1) O(1)-M-N(1) O(2)-M-O(5) O(1)-M-O(5) N(1)-M-O(5) O(2)-M-O(4) O(1)-M-O(4) N(1)-M-O(4) O(5)-M-O(4) O(2)-M-O(3) O(1)-M-O(3) N(1)-M-O(3) O(5)-M-O(3) O(4)-M-O(3)

168.69(9) 97.84(10) 91.16(10) 91.47(9) 94.84(9) 93.33(10) 86.61(9) 86.61(9) 89.68(9) 176.63(8) 91.44(9) 78.65(8) 167.13(10) 95.33(8) 81.96(8)

168.78(17) 98.63(19) 91.06(18) 91.32(17) 93.81(17) 92.99(18) 86.29(16) 88.28(16) 88.91(17) 177.15(16) 89.25(16) 80.38(15) 168.69(17) 94.94(15) 83.48(14)

168.84(13) 98.25(14) 90.86(13) 91.74(13) 94.22(12) 93.12(13) 86.49(12) 87.18(12) 89.28(13) 177.20(12) 90.25(12) 79.83(11) 168.02(14) 95.05(11) 82.79(10)

a Symmetry transformations used to generate equivalent atoms for 1: (#1) -x + 1/2, y - 1/2, z; (#2) x + 1/2, -y + 3/2, -z. b Symmetry transformations used to generate equivalent atoms for 2: (#1) x, -y + 1/2, z - 1/2; (#2) -x + 1, y + 1/2, -z + 1/2. c Symmetry transformations used to generate equivalent atoms for 3: (#1) -x + 1/2, y + 1/2, z; (#2) x - 1/2, -y + 1/2, -z.

Results and Discussion Syntheses. The combination of metal ions with malic acid (hydroxybutane diacid) and 4,4′-bipyridine in an alcohol/water medium at mild temperatures yielded three novel coordination polymers. In M-malate-bipy reaction systems, except the ratio of metal salts with two kinds of ligands, a pH value of 4-5 as well as the volume ratio of water to alcohol of 2-3 is essential for the formation of crystalline products. Moreover, for the Co/ Ni mixed-metal system, we explored the difference of Co:Ni ratio in the product (according to the elemental analyses) by varying the Co:Ni ratio in the reactants. For example, when the molar ratio of Co to Ni in the reactants is 1:1, the molar ratio of Co to Ni in the product is about 1:2, whereas when the ratio of Co to Ni in the reactants is 1:2, the molar ratio of Co to Ni in the product is close to 1:3. The reason might be

Metal-Malate-Bipyridine Coordination Polymers

Crystal Growth & Design, Vol. 6, No. 5, 2006 1103

Figure 1. Coordination environment of M(II) atoms in compounds 1-3.

attributed to the Ni(II) ions combining with bipy molecules more easily than Co(II) ions according to the hard-soft acid-base rule. Crystal Structures. X-ray single-crystal structural analyses reveal that compounds 1-3 possess three-dimensional networks based on [M(C4H4O5)]n layers pillared by 4,4′-bipyridine molecules. The µ3-malate ligand adopts a pentadentate coordination mode (Scheme 1, mode VIII) with all of its five oxygen atoms participating in the coordination, which could stabilize the metal-malate network by forming five- and six-membered rings. As shown in Figure 1, the M(II) ion displays an octahedral coordination environment with one hydroxyl oxygen and four carboxylate oxygen atoms coming from three different malate ligands, and the one remaining position was occupied by a nitrogen atom of the bipy molecule. Taking compound 1 as an example, the bond lengths of Co-O range from 2.031(2) to 2.163(2) Å with an average value of 2.139(2) Å, and the CoN(1) distance is 2.099(3) Å. The angles of O(1)-Co-O(3) and O(3)-Co-O(4) containing the hydroxyl oxygen atom are small, with values of 79.04(7) and 81.59(8)°, respectively, owing to the formation of five- and six-membered chelate rings, whereas other O-Co-O (or N) angles of neighboring oxygen atoms formed at the Co(II) ion range from 86.61(9) to 97.84(10)°. In the three compounds reported here, the malate dianion binds with one metal ion in a fac mode through its hydroxyl oxygen and R- and β-carboxylate oxygen atoms, and the other two oxygen atoms (O2(A) and O5(B)) of the malate ligand coordinate further to two other M(II) atoms in a monodentate fashion. In compound 1, the angles O(1)-C(1)-O2(A) (Rcarboxylate) and O(4)-C(4)-O5(B) (β-carboxylate) are 125.9(3) and 123.3(3)°, respectively. Both R-carboxyl and β-carboxyl groups adopt bidentate bridging modes, coordinating to two metal centers in a nonplanar skew-skew fashion, and the corresponding torsion angles in compound 1 are as follows: C(2)-C(1)-O(1)-Co, -17.33(33)°; C(2)-C(1)-O(2)-Co, 118.35(29)°; C(3)-C(4)-O(4)Co, -39.62(37)°; C(3)-C(4)-O(5)-Co, 169.77(19)°. The corresponding bond lengths and angles of compounds 2 and 3 are close to those of 1. It is noteworthy that four carboxylate oxygen atoms (O1, O2, O4, and O5) from three different malate chains constitute the octahedral equatorial plane (Figure 1), while the oxygen atom of the hydroxyl group and one nitrogen atom of the bipy molecule occupy the axial positions. As a result, the [M(C4H4O5)] moiety could only extend in the ab plane, giving covalentbonded [M(C4H4O5)]n sheets, and the adjacent M‚‚‚M(A)

Figure 2. View of the [Co(C4H4O5)]n layer in the ab plane. Pyridine rings and hydrogen atoms have been omitted for clarity.

Figure 3. View of the 3D network for compounds 1-3 showing the rectangular channels approximately along the [100] direction. All hydrogen atoms have been omitted for clarity.

distances connected by R-carboxylate and M-M(B) distances by β-carboxylate are about 5.4 and 5.0 Å, respectively. As shown in Figure 2, the metal ions were connected by R-carboxylates in the [010] direction and by β-carboxylates in the [100] direction, respectively, to produce infinite [M(C4H4O5)]n layers in the ab plane. The layers themselves are made up of edge-sharing 16-membered rings of four metal cations and four malate anions, and the pyridyl rings arrange in four directions up and down the layers alternately. Furthermore, the neighboring [M(C4H4O5)]n layers are pillared together by neutral bipyridine ligands, leading to the formation of an infinite 3D coordination network. Between the two-dimensional layers, the M‚‚‚M distance linked by one bipy molecule is about 11.2 Å. The bridging bipy molecules can be clearly seen between the layers, enclosing void rectangular channels (Figure 3) parallel to the [100] direction and triangular-shaped channels (Figure 4) parallel to the [010] direction. The pyridine rings of 4,4′-bipyridine are practically planar within experimental error, but the ligand as a whole deviates significantly from planarity, and the dihedral angle between the mean planes of the two pyridyl rings is 26.8°. Magnetic Measurements. The magnetic properties of compounds 1-3 were studied as a function of temperature (2-300

1104 Crystal Growth & Design, Vol. 6, No. 5, 2006

Duan et al.

Figure 4. View of compounds 1-3 showing the triangular-shaped channels along the [010] direction. All hydrogen atoms have been omitted for clarity.

K) in a fixed magnetic field (5000 Oe), and three compounds exhibit antiferro- (1), ferro- (2), and antiferromagnetic (3) interactions between the metal centers, owing to the existence of different magnetically active ions of Co(II), Ni(II), or Co(II)/Ni(II). The thermal dependence of χM and χMT products (χM being the magnetic susceptibility per M(II) ion) is shown in Figure 5a for compound 1. At room temperature, χMT is equal to 2.93 cm3 K mol-1, a value which is greater than that expected for the spin-only one for a high-spin cobalt ion (1.88 cm3 K mol-1 with g ) 2.0) but is close to the value of 3.37 cm3 K mol-1 expected when the spin momentum and the orbital momentum exist independently (µLS ) [L(L + 1) + 4S(S + 1)]1/2, L ) 3, S ) 3/2). This is due to the occurrence of an unquenched orbital contribution typical of the 4T1g ground state in six-coordinated cobalt(II) complexes. Upon cooling, χMT continuously decreases, reaching a minimum value of 1.00 cm3 K mol-1 at 2.0 K. No maximum of susceptibility is observed in the χM versus T plot. As the high-spin octahedral CoII has a 4T1g ground state and, as a consequence, exhibits unquenched spin-orbital coupling in addition to zero-field splitting, this species dominates in the lowtemperature region. Unfortunately, no expressions account for both factors simultaneously. Therefore, the data were fit for spin-orbital coupling. The molecular field approximation was further considered as magnetic interactions between cobalt(II) ions:

χM )

[

2 2 Nβ2 7(3 - A) x 12(A + 2) + + 3kT 5 25A 2(11 - 2A)2x 176(A + 2)2 5Ax + exp + 45 675A 2 (A + 5)2x 20(A + 2)2 exp(-4Ax) 9 27A x 5Ax 3 + 2 exp + exp(-4Ax) 3 2

{

{

[[

}

}

(

(

)

]/

)

]]

χM ) χCo/[1 - χCo(2zJ′/Ng2β2)] In this expression, zJ′ is the exchange parameter and the rest of the parameters have their usual meanings. The best fit is obtained with values of A ) 1.4, λ ) -151 cm-1, g ) 2.11, and zJ′ ) -0.52 cm-1, where A is a crystal field parameter (A

Figure 5. Temperature dependence of χM and χMT (insert) for compounds 1 (a, top) and 2 (b, bottom). The solid lines are the best fits with the parameters in the text.

) 1.5 is the weak-field limit) and λ is the spin-orbital coupling constant (λ ) -176.0 cm-1 is the free-ion value); the agreement factor R ) 2.12 × 10-3. The magnetic behavior of compound 2 under the form of χM and χMT versus T plots is shown in Figure 5b. At room temperature χMT is 1.14 cm3 K mol-1, which is slightly higher than that for a spin-only Ni(II) ion (1.00 cm3 K mol-1 with g ) 2.0). This value continuously increases on cooling, reaches a maximum value of 2.57 cm3 K mol-1 at 3 K, and then abruptly decreases to 2.04 cm3 K mol-1 at 2 K. This curve is in agreement with a significant ferromagnetic coupling between nickel ions, which have been observed in some compounds through the anti-syn carboxylate-bridged nickel(II).13 The absence of a susceptibility maximum in the χM versus T plot indicates that the decrease of χMT is mainly due to zero-field splitting (D). To determine the ferromagnetic coupling observed in this compound, we have fitted the experiment magnetic data by the Fisher equation, including the zero-field splitting:14,15

ΧM ) χZFS(1 + µ)/(1 - µ) µ ) coth[JS(S + 1)/kT] - [kT/JS(S + 1)] χZFS ) (χ| + χ⊥)/3 2Ng|2β2 exp(-D/kT) χ| ) ‚ kT 1 + 2 exp(-D/kT)

Metal-Malate-Bipyridine Coordination Polymers

χ⊥ )

2Ng⊥2β2 1 - exp(-D/kT) ‚ kT 1 + 2 exp(-D/kT)

On the assumption that g| ) g⊥ ) g, the best-fit parameters were g ) 2.09, J ) 3.5 cm-1, D ) -0.77 cm-1, and R ) 3.2 × 10-3. The thermal dependence of χM and χMT products for compound 3 is shown in Figure 6. The magnetic susceptibility above 50 K obeys the Curie-Weiss law with C ) 1.75 cm3 K mol-1 and Θ ) -3.70 K, which suggests antiferromagnetic interactions between metal ions through the malate carboxylate bridges. The χMT value at 300 K is 1.71 cm3 K mol-1, which is higher than that expected for the total value (1.26 cm3 K mol-1 assuming g ) 2.0 for CoII and NiII) of uncoupled 0.3CoII (S ) 3/2) and 0.7NiII (S ) 1). When the temperature is lowered, the χMT value decreases slowly and remains constant at 1.56 cm3 K mol-1 from -24 to -12 K, it then has a slight increase followed by an abrupt decrease, reaching 1.33 cm3 K mol-1 at 2 K. The magnetic behavior of compound 3 should be attributed to the simultaneous action of Co(II) and Ni(II) ions; however, it is difficult to fit the experimental magnetic data of this threedimensional mixed-metal system using a suitable theoretical model. It should be noted that the magnetic pathways of the three compounds are through M-O-C-O-M with the same conformations, but they have different magnetic behaviors, which are related to their metal centers as well as the malate carboxylate bridges. Different electronic configurations of the metal ions involving three (1) and two (2) unpaired electrons could account for the fact13a,14 that the magnetic couplings between cobalt(II) or nickel(II) ions are antiferro- and ferromagnetic for compounds 1 and 2, respectively. As the ferromagnetic couplings in 2 are very weak, the presence of one unpaired electron in the t2g type orbital for 1 would increase the possibility of net overlap between the magnetic orbitals, thus enhancing the antiferromagnetic contributions in 1 and the ferromagnetic terms would be overcome. Other Characterization Data. According to the charge balance, we assign O(3) atoms in three compounds as hydroxyl oxygen rather than alkoxyl oxygen atoms; this assignment is also confirmed by the BVS calculations16 (1.00 for compound 1 and 1.11 for 2). The oxidation state of the metal ions is considered to be +2, according to the structural analyses and XPS data, which give electronic binding energies of 781.0 eV for 1 and 855.4 eV for 2 attributable to Co(II) 2p3/2 and Ni(II) 2p3/2, respectively, while the peaks at 782.8 and 856.9 eV for 3

Figure 6. Temperature dependence of χM (O) and χMT (9) for compound 3.

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indicate the coexistence of Co(II) and Ni(II). The thermal behaviors of three compounds were studied from 30 to 800 °C in air, and they have similar thermal stabilities. In compound 2, for example, the weight loss of 6.1% from 50 to 162 °C is close to the loss of one lattice water molecule (6.3%). The host framework remains stable up to 320 °C, and then the dehydrated sample decomposes rapidly accompanied by an obvious exothermic process, undoubtedly due to the combustion of organic malate and bipyridine ligands. The decomposition is complete at 440 °C, resulting in the formation of nickel oxide as a residue. Conclusion The work reported here has focused on the construction of novel 3D frameworks and magnetic behaviors of the solid materials. The ratio of metal salts with malate and bipy ligands as well as the volume ratio of alcohol with water in the reaction system is important for the formation of crystalline products. Three compounds have different magnetic behaviors related to the metal centers and the magnetic pathways of carboxylate bridges. The successful design and syntheses of these metalmalate-bipy, metal-malate, and metal-citrate coordination polymers6-8 confirm once more that the HPCs can act as suitable candidates in the construction of novel networks, and they provide an appropriate strategy to explore the structures and magnetic properties of metal-HPC coordination polymers. Acknowledgment. This work was supported by the National Natural Science Foundation of Chain (No. 2001CB108906) and the National Natural Science Foundation of China (Nos. 20571032 and 20333070). Supporting Information Available: X-ray crystallographic data as CIF files. This material is available free of charge via the Internet at http://pubs.acs.org.

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