A Three-Dimensional Hetero-Bimetallic Coordination Polymer with

Apr 17, 2014 - China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 21...
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A Three-Dimensional Hetero-Bimetallic Coordination Polymer with Unusual (4,5)-Connected Topology and Ferrimagnetic Property Based on Octacyanotungstate and Polydentate Ligand Jun Qian,† Jingchun Hu,† Hirofumi Yoshikawa,‡,⊥ Jinfang Zhang,† Kunio Awaga,‡,⊥ and Chi Zhang*,† †

China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 212013, P. R. China ‡ Research Center for Materials Science, Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan S Supporting Information *

ABSTRACT: A three-dimensional (3D) manganese−tungsten bimetallic coordination polymer (CP) {{[μ 5 -W(CN) 8 ] 2 [Mn(HMTA)1.5]2[Mn(HMTA)(H2O)2]}·2H2O}n (CP-1) (HMTA = hexamethylenetetramine) is constructed by the reaction of the molecular building block [W(CN)8]3− and tetradentate bridging ligand HMTA with d5 transition metal ion Mn2+. CP-1 has been unambiguously confirmed by Fourier-transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal and powder X-ray diffraction. Crystallographic analysis reveals that, crystallizing in the monoclinic crystal system with P21/c space group, CP-1 possesses an infinite 3D framework and exhibits an unusual (4,5)-connected 4,5T7 topology with point symbol (32·62·72)(3·44· 52·62·7)4. The extended 3D structure is constructed by twodimensional (2D) cyano-bridged corrugated -W−Mn2−W−Mn2layers pillared via the [Mn1(HMTA)(H2O)2] units. The magnetic investigation indicates ferrimagnetic behavior for CP-1 because of the antiferromagnetic coupling between WV (S = 1/2) and MnII (S = 5/2) centers mediated by cyano bridges.

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INTRODUCTION

choice of metal-containing molecular building blocks is becoming more and more seductive.4 The octacyanometalates [M(CN)8]3−/4− (M = W, Mo, Nb), as a sort of polydentate molecular building block, have been extensively used for assembly of heterobimetallic CPs with diverse topological structures and magnetic interactions between metal centers, owing to their novel geometric structures and appealing magnetic properties.5 In particular, [M(CN)8]3−/4− can be viewed as a class of versatile metalcontaining molecular building blocks, which can adopt three different spatial configurations: square antiprism (D4d), dodecahedron (D2d), or bicapped trigonal prism (C2v), depending on the external coordinated environment. It has been well-documented that a number of [M(CN)8]-based bimetallic CPs with rich magnetic properties, such as singlemolecule magnets (SMMs),6 photomagnets,7 and long-range ordered magnets,8 have been prepared and investigated. Nevertheless, only a few [M(CN)8]-based CPs have been studied intensively from the viewpoint of topological structures.9 To our knowledge, the major topological types of

In recent years, significant attention has been paid to crystal engineering of functional coordination polymers (CPs) due to their intriguing topologies and potential application as functional materials in many areas, such as catalysis, gas storage, and optoelectronic and magnetic properties.1 Many efforts in this field are focused on the design and preparation of functional molecules and materials, as well as the investigation of structure−function correlation. Although a large number of CPs have been constructed thus far by various organic linkers and metal centers, rational control of coordination networks still remains a great challenge in crystal engineering.2 It has been documented that the most successful strategy for constructing coordination polymers is based on the assembly of molecular “building blocks” that are constituted of metalcontaining molecular units and bridging organic linkers. For example, the carboxylic acids, diamines, and polypyridine derivatives have witnessed the most important development of CPs owing to their rich coordination modes.3 The development of new organic linkers that fulfill the requirements of “building blocks” for the construction of CPs is still in progress. On the other hand, as the metal component plays an important role in constructing functional CPs, the judicious © 2014 American Chemical Society

Received: December 20, 2013 Revised: April 14, 2014 Published: April 17, 2014 2288

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prior to use, and other chemicals were generally used as commercially available. Caution! The preparation of (Bu3NH)3[W(CN)8] in the acid reaction condition is potentially dangerous for health, and the manipulations should be handled very carefully in a fume hood. Synthesis of {{[μ 5 -W(CN) 8 ] 2 [Mn(HMTA) 1.5 ] 2 [Mn(HMTA)(H2O)2]}·2H2O}n CP-1. The reaction of MnCl2·4H2O (30 mg, 0.15 mmol) and HMTA (28 mg, 0.20 mmol) in 3 mL of water resulted in a pale pink solution. After stirring and subsequent filtration, a mixed solution of H2O and methanol (v/v = 1:2, 3 mL) was layered gently on the top of the filtrate. After that, a solution of (Bu3NH)3[W(CN)8] (112 mg, 0.10 mmol) dissolved in 3 mL of methanol was added carefully as the third layer. The resulting solution stood undisturbed in the dark at room temperature. After slow diffusion for several weeks, dark block crystals of CP-1 were obtained with a yield of 40% (63 mg, based on W). Anal. Calc. for C40H56Mn3N32O4W2: C, 29.75; N, 27.87; H, 3.49%. Found: C, 29.83; N, 27.96; H, 3.50%. IR (KBr, cm−1, Figure S4, Supporting Information): 3409(br), 2961(sh), 2186(w), 2121(s), 1634(w), 1465(m), 1384(m), 1237(m), 1228(sh), 1019(sh), 1005(sh), 831(m), 695(m). Single-Crystal Structure Determination. A suitable single crystal of dimension 0.25 × 0.22 × 0.20 mm for CP-1 was selected and mounted in air onto thin glass fibers. The diffraction data were measured with Mo Kα radiation (λ = 0.71070 Å) on a Rigaku AFC10 Saturn-70 CCD diffractometer. The SMART and SAINT program packages were used for data collection and integration, respectively. Collected data were corrected for absorbance using SADABS based upon Laue symmetry using equivalent reflections. Its structure was solved by direct methods and refined on F2 by full-matrix least-squares calculations with the using SHELX-97.16 All of the non-hydrogen atoms were refined with anisotropic thermal displacement coefficients. The hydrogen atoms of H2O and HMTA were refined isotropically and placed at calculated positions. The monodentate HMTA (C19) molecules are highly disordered, and an attempt to locate H atoms on the calculated positions by riding method was unsuccessful. Crystallographic data of CP-1 are summarized in Table 1, while the selected bond distances and angles are listed in Table 2.

[M(CN)8]-based assemblies are mainly based on 4-, (4,6)-, or (4,8)-connected frameworks,7a,d,8a,b,9,10a,17 while the 5-, (3,5)-, and (4,5)-connected networks5d,e,g,8c,10b are relatively scarce among the reported examples. As for the bridging organic linkers, although a large amount of new organic ligands have been developed for the construction of coordination polymers, the application of some existing organic linkers has not been fully realized.6f,11 For example, HMTA can be considered as a good molecular “building block”, owing to the fact that HMTA may adopt four distinct coordination geometries including the monodentate and μn-bridging (n = 2−4) modes (Scheme 1) and can Scheme 1. Coordination Modes of HMTA Bridging Unit

therefore act as a polydentate bridging ligand, for the construction of topologically interesting metal−HMTA architectures.11−13 In addition, attributed to its good hydrogen-bond accepting behavior, HMTA often forms a variety of molecular adducts and supramolecular structures with hydrogen-donor groups via the hydrogen bonds.11a,12g Accordingly, a large number of HMTA-driven polymers comprising different metals have been reported.11a,12,13 However, most of such CPs are structurally characterized as monometallic assemblies, and to the best of our knowledge, only four HMTA-driven CPs possess bimetallic skeletons.14 In contrast to its various coordination capabilities, HMTA as a polydentate bridging linker for constructing bimetallic CPs with topologically interesting architectures remains largely unexplored to date. In this study, by applying metal-based molecular building block [W(CN)8]3− and a polydentate bridging linker−HMTA, we report the self-assembly and structure study of a threedimensional (3D) HMTA-driven heterobimetallic coordination polymer {{[μ 5 -W(CN) 8 ]2 [Mn(HMTA)1.5 ]2 [Mn(HMTA)(H2O)2]}·2H2O}n (CP-1), which exhibits an unusual 2-nodal (4,5)-connected 4,5T7 topology with point symbol (32·62· 72)(3·44·52·62·7)4. Variable-temperature magnetic susceptibility study of CP-1 indicates the presence of ferrimagnetic interaction due to the antiferromagnetic coupling between WV (S = 1/2) and MnII (S = 5/2) centers mediated by cyano bridges.

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Table 1. Crystal Data and Structure Refinement for CP-1 formula

C40H56Mn3N32O4W2

Mr (g mol−1) crystal system space group temperature (K) a (Å) b (Å) c (Å) β (deg) V (Å3) Z Dcalc (g cm−3) μ (mm−1) R(int) GOF R1 [I > 2σ(I)] wR2 [I > 2σ(I)] reflections collected/unique Δρmax (e·Å−3) Δρmin (e·Å−3)

1581.67 monoclinic P21/c 293(2) 7.3941(15) 15.280(3) 23.345(5) 106.30(3) 2531.5(9) 2 2.075 5.334 0.0284 1.136 0.0518 0.1362 11952/4896 2.232 −1.996

Physical Measurements. The elemental analysis for carbon, hydrogen, and nitrogen was performed on a Perkin-Elmer 240C elemental analyzer. Infrared spectrum was recorded with a Nicolet FT170SX Fourier transform spectrometer (KBr pellets). The thermogravimetric analysis (TGA) was performed in an air atmosphere from room temperature to 1200 °C by a Perkin-Elmer Pyris 1 system with a

EXPERIMENTAL SECTION

Materials. All reactions and manipulations were conducted in an air atmosphere except when especially mentioned. The original material (Bu3NH)3[W(CN)8] was synthesized according to the literature procedure.15 The solvents were roughly dried and distilled 2289

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Table 2. Selected Bond Distances (Å) and Angles (deg) of CP-1a W(1)−C(7) W(1)−C(4) W(1)−C(8) W(1)−C(1) W(1)−C(2) W(1)−C(3) W(1)−C(5) W(1)−C(6)

2.140(10) 2.144(10) 2.157(10) 2.162(11) 2.170(10) 2.188(10) 2.191(10) 2.192(11)

Mn(1)−N(4) 2.165(8) Mn(1)−N(4)#1 2.165(8) Mn(1)−O(1)#1 2.196(7) Mn(1)−O(1) 2.196(7) Mn(1)−N(11)#1 2.377(8) Mn(1)−N(11) 2.377(8) N(4)−Mn(1)−N(4)#1 N(4)−Mn(1)−O(1)#1 N(4)#1−Mn(1)−O(1)#1 N(4)−Mn(1)−O(1) N(4)#1−Mn(1)−O(1) O(1)#1−Mn(1)−O(1) N(4)−Mn(1)−N(11)#1 N(4)#1−Mn(1)−N(11)#1 O(1)#1−Mn(1)−N(11)#1 O(1)−Mn(1)−N(11)#1 N(4)−Mn(1)−N(11) N(4)#1−Mn(1)−N(11) O(1)#1−Mn(1)−N(11) O(1)−Mn(1)−N(11) N(11)#1−Mn(1)−N(11)

N(1)−C(1) N(2)−C(2) N(3)−C(3) N(4)−C(4) N(5)−C(5) N(6)−C(6) N(7)−C(7) N(8)−C(8)

1.127(13) 1.159(13) 1.149(13) 1.142(13) 1.131(13) 1.143(14) 1.147(13) 1.135(13)

N(1)−C(1)−W(1) N(2)−C(2)−W(1) N(3)−C(3)−W(1) N(4)−C(4)−W(1) N(5)−C(5)−W(1) N(6)−C(6)−W(1) N(7)−C(7)−W(1) N(8)−C(8)−W(1)

Mn(2)−N(7)#2 Mn(2)−N(1)#3 Mn(2)−N(8)#4 Mn(2)−N(6) Mn(2)−N(13) Mn(2)−N(10) 180.00(17) 91.1(3) 88.9(3) 88.9(3) 91.1(3) 180.0(4) 90.6(3) 89.4(3) 91.0(3) 89.0(3) 89.4(3) 90.6(3) 89.0(3) 91.0(3) 180.000(2)

2.168(8) C(1)−N(1)−Mn(2)#5 2.177(9) C(4)−N(4)−Mn(1) 2.214(8) C(6)−N(6)−Mn(2) 2.245(10) C(7)−N(7)−Mn(2)#6 2.289(12) C(8)−N(8)−Mn(2)#7 2.412(8) C(13)−N(10)−Mn(2) C(10)−N(10)−Mn(2) C(14)−N(10)−Mn(2) C(10)−N(11)−Mn(1) C(12)−N(11)−Mn(1) C(11)−N(11)−Mn(1) N(8)#4−Mn(2)−N(6) N(7)#2−Mn(2)−N(13) N(1)#3−Mn(2)−N(13) N(8)#4−Mn(2)−N(13) N(6)−Mn(2)−N(13) N(7)#2−Mn(2)−N(10) N(1)#3−Mn(2)−N(10) N(8)#4−Mn(2)−N(10) N(6)−Mn(2)−N(10) N(13)−Mn(2)−N(10)

177.0(9) 178.7(10) 177.1(9) 176.6(9) 177.9(10) 177.2(10) 176.4(9) 176.1(9)) 161.9(9) 163.6(9) 171.4(9) 163.1(8) 171.6(8) 112.4(6) 106.6(6) 113.4(6) 110.7(6) 114.0(6) 108.2(6) 178.2(3)) 88.5(4) 92.5(4) 90.0(4) 90.5(4) 88.4(3) 90.7(3) 84.3(3) 95.2(3) 173.5(4)

Symmetry transformations used to generate equivalent atoms of CP-1. #1: −x, −y − 1, −z − 1. #2: −x, y − 1/2, −z − 1/2. #3: x + 1, y, z. #4: −x + 1, y − 1/2, −z − 1/2. #5: x − 1, y, z. #6: −x, y + 1/2, −z − 1/2. #7: −x + 1, y + 1/2, −z − 1/2. #8: x, −y − 1/2, z + 1/2. #9: x, −y − 1/2, z − 1/2. #10: −x + 1, −y − 1, −z. a

heating rate of 10 °C/min (Figure 7). The powder X-ray study (Figure S3, Supporting Information) was recorded on a XD-3 diffractometer equipped with a 3 kW sealed tube Cu Kα X-ray diation (generator power settings: 35 kV and 20 mA) and a DTex Ultra detector using the parallel beam geometry (5° primary and 80° terminated, 3° divergence slit with 10 mm height limit slit). The temperature dependence of molar magnetic susceptibility was measured under an applied field of 1000 G in the form of χmT versus T in the range of 2− 300 K by Quantum Design MPMS XL-5. The influence of sample holder background was subtracted by the automatic subtraction feature of the software.

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Scheme 2. Preparation of CPs from Mn2+ and HMTA Based on Two Different Molecular “Building Blocks”

RESULTS AND DISCUSSION

Synthetic Procedure. According to the literature, the most common synthetic strategies for the HMTA-driven CPs are based on facile self-assembly reactions in aqueous medium.12g As shown in Scheme 2, the reaction of Mn2+ and HMTA in the presence of organic linker malonate afforded a 3D CP [Mn2(HMTA)(mal)2(H2O)2]n with weak antiferromagnetic property.12b The organic ligand malonate herein acts as another polydentate bridging linker for the construction of the 3D framework. However, in contrast to the above aqueous selfassembly, the octacyanometalate (Bu3NH)3[W(CN)8], which is introduced as the polydentate bridging “metalloligand” into the self-assembly of HMTA-driven heterobimetallic CPs, is a water-insoluble staring material. Accordingly, it is difficult to achieve a homogeneous reaction environment for all reactants

and thereby to obtain suitable single crystals for X-ray diffraction analysis in single aqueous solution. Given the fact that the precursor (Bu3NH)3[W(CN)8] cannot be dissolved in water to form a clear solution, the mixed solvent edge-diffusion method was introduced into the selfassembly of HMTA-driven CPs.9g In this reaction, the MnCl2· 4H2O and HMTA were first mixed in aqueous solution, while the (Bu3NH)3[W(CN)8] was dissolved in methanol. The treatment of MnCl2·4H2O with HMTA in a 3:4 molar ratio in 2290

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water resulted in a pale pink solution, which can keep stably and clearly even if the resultant pink solution is stirred for a long time. By employing the H2O/CH3OH (v/v = 1:2) mixture as a buffer, CP-1 was obtained from the diffusion reaction between the water-insoluble precursor (Bu3NH)3[W(CN)8] and the mixture of MnCl2·4H2O and HMTA. In the selfassembly process of CP-1, the H2O/CH3OH mixture plays an important role in providing a stable environment for the diffusion reaction of three starting materials. In contrast with the above [Mn2(HMTA)(mal)2(H2O)2]n, the resulting CP-1 not only represents a new HMTA-driven heterobimetallic CPs but also exhibits the typical ferromagnetic property (Scheme 2). Structural Analysis of CP-1. The single-crystal X-ray structural analysis shows that CP-1 crystallizes in the monoclinic crystal system with the space group of P21/c (Table 1) and possesses an infinite 3D framework with the 2nodal (4,5)-connected 4,5T7 topology. The overall structure of CP-1 can be viewed as two-dimensional (2D) wavelike cyanobridged -W−Mn2−W−Mn2- layers sustained by [Mn1(HMTA)(H2O)2] pillar units via both μ-CN− bridges and μ2HMTA linkers to create a consecutive 3D architecture (Figure 4d). As shown in Figure 1, each W atom of the building block [W(CN)8]3− is connected with four Mn2 atoms and one Mn1

Figure 2. Coordination mode of Mn1 atom in CP-1, showing the 4connecting mode (W, green; Mn1, purple; Mn2, red; C, gray; N, blue; O, cyan). All hydrogen atoms are omitted for clarity.

Figure 3. Coordination mode of Mn2 atom in CP-1, showing the 5connecting mode (W, green; Mn1, purple; Mn2, red; C, gray; N, blue; O, cyan). All hydrogen atoms are omitted for clarity.

coordination modes, namely, μ2-HMTA and the terminal HMTA. In comparison to the Mn1 atom, each Mn2 atom is linked with four [W(CN)8]3− building blocks via μ-CN− bridges and one Mn1 atom through HMTA ligand and also exhibits a 5-connecting mode. In accordance with Figure 4b, the connection of building blocks [W(CN)8]3− and Mn2 atoms via μ-CN− groups forms a 2D wavelike -W−Mn2−W−Mn2- layer network from the b axis. In this 2D structure, two W atoms and two Mn2 atoms are linked by μ-CN− bridges to build a tetragonal lattice (Figure 4a), which leads to the whole 2D layer structure showing a (4,4) network. These 2D layers are further extended to the 3D framework via the [Mn1(HMTA)(H2O)2] units (Figure 4c), which can be regarded as the pillars of the 3D structure. The packing diagram showing the 3D extending structure of CP-1 is displayed in Figure 4d. As shown in Figure 4d, the Mn1 atoms are connected with the 2D wavelike -W−Mn2−W−Mn2- layer via both μ-CN− bridges and μ2-HMTA ligands. In the 3D framework, a kind of 12-membered metal ring exists (Figure 5 a ) , w h i c h is si m i l a r t o t h e r e p o r t e d 2 D C P {[MnII(DMF)4]3[MoV(CN)8]2}n.17 Although these two kinds of rings are both constructed by building blocks [M(CN)8]3− (M = W, Mo) linked via Mn atoms, the ring in such a 3D

Figure 1. Coordination mode of W atom in CP-1, showing the 5connecting mode of [W(CN)8]3− unit (W, green; Mn1, purple; Mn2, red; C, gray; N, blue; O, cyan). All hydrogen atoms are omitted for clarity.

atom via the μ-CN− bridges, showing a 5-connecting mode. The infrequent 5-connecting mode of W atom leads to a distorted bicapped trigonal prism spatial configuration. In accordance with Figure 2, each Mn1 atom is coordinated with two O atoms from H2O molecules and four N atoms from μCN− bridges and μ2-HMTA bridged ligands, respectively, exhibiting an octahedral geometry. The six-coordinated Mn1 atom is linked with two W atoms via two μ-CN− groups and two Mn2 atoms through two μ2-HMTA bridging ligands, showing a 4-connecting mode. Each Mn2 atom, as in Figure 3, is coordinated by six N atoms: four N atoms from μ-CN− bridges of four different building octacyanometalates [W(CN)8]3−, one from a terminal HMTA ligand and one from a μ2-HMTA bridged ligand, respectively. It is obviously that the HMTA ligands in CP-1 adopt two different kinds of 2291

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1.159(13) Å. The bond angles of W−C−N are almost linear with the value ranging from 176.1(9)° to 178.7(10)°. For C− N−Mn angles, the bond angles of C−NHMTA−Mn vary from 106.6(6)° to 114.0(6)°, while the C−NCN-Mn bond angles fall in the range of 161.9(9)−171.6(8)°. As for Mn−N bond, the Mn−NHMTA bond lengths vary from 2.289(12) Å to 2.412(8) Å, which are obviously longer than the distances of Mn−Ncyano in the range of 2.165(8)−2.214(8) Å. It is noticed that the Mn1−Ncyano bond length (2.165(8) Å) is shorter than the average value of Mn2−Ncyano (2.209(9) Å), while the bond length of Mn1−Nμ‑HMTA (2.377(8) Å) is also shorter than the value of Mn2−Nμ‑HMTA (2.412(8) Å). In accordance with the literature, the Mn−N bond lengths of CP-1 are similar to the value of other examples,6a,9c−e while the bond length of Mn1− O (2.196(7) Å) is also close to the reported data.17 The topological structure of CP-1 has been analyzed in detail by both TOPOS and OLEX programs (Figure 6).18 The results Figure 4. (a) Quadrilateral structure constructed by two [W(CN)8]3− units and two Mn2 atoms. (b) 2D wavelike structure of -W−Mn2− W−Mn2- layer. (c) [Mn1(HMTA)(H2O)2] unit. (d) Packing structure of CP-1 along the a axis direction. All hydrogen atoms are omitted for clarity.

Figure 6. Topological structure of CP-1 (W, green; Mn1, orange; Mn2, purple). (Point symbol is {32·62·72}{3·44·52·62·7}4.)

demonstrate that both the point symbol of the 5-connecting W and Mn2 atoms are (3·44·52·62·7), while the point symbol of the 4-connected Mn1 atom is (32·62·72). According to the molar ratio of W nodes, Mn2 nodes and Mn1 nodes (2:2:1), the topological network of CP-1 can be described by the point symbol of (32·62·72)(3·44·52·62·7)4, with the extended point symbol of (3·3·6·6·74·74)(3·4·4·4·4·5·5·62·62·73)4, which indicates a 2-nodal (4,5)-connected 4,5T7 topology. The sides of new topology are formed by μ-CN− bridges and μ2-HMTA ligands. Although a handful of (4,5)-connected networks have been reported and categorized by O’Keeffe et al.,19 for example, bnn-a, ctn-x, ffa, ffb, gar-a, iac-a, ibd-a, mcf-d, nia-a, ocu-a, rtw, scu-f, sqp-a, tcs, and toc-a,20 to the best of our knowledge, CP-1 composing the first HMTA-based CP with a 4,5T7 net not only represents a new WVMnII HMTA-driven heterobimetallic framework but also acts as a rare example among metal−organic frameworks (MOFs).5d,g,8c Thermogravimetric Analysis. The thermogram for CP-1 was recorded in Figure 7. It is observed that the CP-1 loses 4.84% weight from room temperature to 170 °C. The weight loss observed below 170 °C can be attributed to the solvent and coordinated molecules (H2O) of CP-1, which is approximately in accord with the result (4.55%) that determined by the single-

Figure 5. (a) The 12-membered metal ring in the structure of CP-1. (b) Packing structure of CP-1 without HMTA. (c) Corresponding topological structure of CP-1 without HMTA. All H2O and HMTA molecules have been omitted for clarity.

structure is definitely distinct from that of the reported one. As illustrated in Figure 5a, the W atoms in CP-1 are connected by both single -CN−Mn1−CN- bridges and double -CN−Mn2− CN- bridges, while the rings in reported 2D structure are only composed of Mo atoms and single -CN−Mn−CN- bridges. The connection between building blocks [W(CN)8]3− and Mn2+ ions here can also lead to a consecutive 3D framework (Figure 5b), which shows a 2-nodal topological structure with the point symbol (44·66)(43·62·8)2 (Figure 5c). Attributed to the 5-connecting mode of Mn2 atoms, the terminal HMTA ligands appear in the two sides of the 2D -W−Mn2−W−Mn2layer (Figure S2, Supporting Information). The selected crystallographic parameters of CP-1 are listed in Table 2. The lengths of W−C bonds range from 2.140(10) to 2.192(11) Å, while the C−N distances vary from 1.127(13) to 2292

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25 cm3 mol−1 K around 20 K. The transformation trend of χmT curve below 50 K illustrates the ferrimagnetic behavior due to an antiferromagnetic coupling between MnII (S = 5/2) and WV (S = 1/2) spin centers. For the temperature range 50−300 K, the inverse magnetic susceptibility data were fitted with the Curie−Weiss Law [χm = C/(T − θ)], affording the parameter of θ = +4.4 K. Corresponding with the χmT curve, the positive Weiss constant θ further confirms the apparent existence of ferrimagnetic interaction in CP-1.8f,21

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CONCLUSIONS In summary, by applying the metal-containing molecular building block [W(CN)8]3− and tetradentate bridging organic linker (HMTA), a new three-dimensional heterobimetallic coordination polymer 1 with 2-nodal (4,5)-connected 4,5T7 topological structure has been constructed and well-characterized. The unique V-shaped bridging mode of μ2-HMTA ligand and unusual 5-connecting mode of [W(CN)8]3− building block play an important role in the construction of such a 3D framework and accordingly affect its final magnetic properties. Attributed to an antiferromagnetic coupling between MnII (S = 5/2) and WV (S = 1/2) spin centers, CP-1 shows the typical ferrimagnetic property with the θ value of +4.4 K in Curie− Weiss Law [χm = C/(T − θ)]. The further investigation on various functionalized coordination polymers based on metalcontaining molecular building blocks and bridging organic linkers μn-HMTA is currently underway in our laboratory.

Figure 7. Thermogravimetric curve of CP-1. The TG curve shows that CP-1 releases four H2O molecules per formula unit below 170 °C.

crystal X-ray structural analysis. The weight losses of 25.04% in the second step from 170 to 440 °C and the subsequent pyrolysis process (26.04%) in the range of 440−700 °C are assigned to the decomposition of the framework. Powder X-ray Diffraction. The powder X-ray diffraction (PXRD) has also been applied to check the phase purity of the bulk samples of CP-1 in the solid state. As illustrated in Figure S3, Supporting Information, the experimental XRD pattern basically matches the simulated pattern, which was generated from the result of single-crystal X-ray diffraction data, indicating the phase purity of product CP-1. Magnetic Properties. The temperature-dependent magnetic susceptibility measurement of the crystalline sample of CP 1 was carried out from 2 to 300 K under an applied field of 1000 G and plotted in the form of χmT versus T in Figure 8. At

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ASSOCIATED CONTENT

* Supporting Information S

X-ray crystallographic information file (CIF) and topological analysis are available for CP-1 (CCDC No.: 921978). Additional figures related to detailed structures (Figures S1− S2), the powder X-ray diffraction pattern (Figures S3) and the IR absorption spectra (Figures S4) are also presented. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*(C.Z.): E-mail: [email protected]; fax: +86-511-88797815. Notes

The authors declare no competing financial interest. ⊥ H.Y. and K.A. contributed to the magnetic properties of this work (H.Y.: e-mail, [email protected]; fax: +81-52-431789-5106).

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ACKNOWLEDGMENTS Financial support from the National Natural Science Foundation of China (Grants 50925207 and 51172100), the Ministry of Science and Technology of China for the International Science Linkages Program (Grants 2009DFA50620 and 2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (Grant IRT1064), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (Grant B13025), and Jiangsu Innovation Research Team is gratefully acknowledged. H.Y. and K.A. are grateful to the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan for a Grant-in-Aid for Scientific Research.

Figure 8. χmT vs T plot for {{[μ5-W(CN)8]2[Mn(HMTA)1.5]2[Mn(HMTA)-(H2O)2]}·2H2O}n CP-1.

room temperature, the χmT value is 14.56 cm3 mol−1 K, which is little higher than the expected spin-only value (13.88 cm3 mol−1 K) of three isolated MnII (S = 5/2) ions and two isolated WV (S = 1/2) ions with g = 1.94. As the temperature decreases, the χmT value basically remains invariant from 300 to 50 K. Below 50 K in temperature, the χmT increases slowly along with cooling, and then it increases sharply to the maximum value of 2293

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