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Nov 2, 2009 - 9. 5351–5355. Heterobimetallic Tungsten/Molybdenum(IV)-Copper(II) MOFs. Constructed by a Unique 2D f 3D Architecture and Exhibiting Ne...
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DOI: 10.1021/cg9008834

Heterobimetallic Tungsten/Molybdenum(IV)-Copper(II) MOFs Constructed by a Unique 2D f 3D Architecture and Exhibiting New Topology and Magnetic Properties

2009, Vol. 9 5351–5355

Jun Qian,† Hirofumi Yoshikawa,§ Jinfang Zhang,‡ Huajian Zhao,† Kunio Awaga,*,§ and Chi Zhang*,†,‡ †

Molecular Materials Research Center, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China, ‡China-Australia Joint Research Center for Functional Molecule Materials, Scientific Research Academy, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, P. R. China, and §Research Center for Materials Science, Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan Received July 28, 2009; Revised Manuscript Received October 14, 2009

ABSTRACT: The present study describes the designed synthesis, X-ray structures, and magnetic properties of two 3D cyanobridged heterobimetallic tungsten/molybdenum(IV)-copper(II) MOFs, {[μ4-M(CN)8]Cu2(DPP)4}n (M=W 1, Mo 2; DPP = 1,3Di(4-pyridyl)propane). Both MOFs 1 and 2 were constructed by interdiffusion approach in two steps: the first reaction of CuSCN and NH4SCN with the flexible bridging ligand DPP in polar solvent for building a 2D homometallic Cu polymer, and the thereafter conformation of 3D heterobimetallic MOF architectures with [M(CN)8]3- and 2D coordination networks. MOFs 1 and 2 are isomorphous and both crystallize in the tetragonal system and have space group I41/a, with unit cell constants a=19.734(3) A˚, b= 19.734(3) A˚, c = 13.989(2) A˚ for 1, and a=19.7429(19) A˚, b = 19.7429(19) A˚, c = 13.9883(15) A˚ for 2. Our study demonstrates that such heterobimetallic MOFs possess a unique 2D f 3D architecture and exhibit a new 2-nodal topological structure. The magnetic measurement of MOFs shows typical paramagnetic properties and weak ferromagnetic interactions. Introduction Metal-organic frameworks (MOFs) by self-assembly are currently attracting considerable attention for their rich variety of intriguing topological structures and great potential applications toward functional materials.1 The most important goal in this field is to reach a real “design” of MOFs with required structures and tailored properties from individual precursors.2 Thus far, most of the MOFs are constructed by diversiform organic linkers and metal centers, the latter including transition metal salts or metal-based secondary building uints (SBUs) with different geometries.1b,2a,3 In contrast to organic ligands, the metal component plays a key role in influencing the physical properties of the metalorganic systems.4 However, the majority of these MOFs are homometallic and constructed by only one kind of metal.5 Recently, coordination complexes or “metalloligands” in lieu of simple organic ligands have been suggested as a promising approach to construct functionalized MOFs.1a,6 It is noteworthy that octacyanometalates [M(CN)8]3(M = W, Mo) are well-known molecular building blocks for transition metal complex-assemblies, because of their various geometric structures and fetching physical properties, such as photo-magnetism and slow magnetic relaxation.7 Although a number of coordination polymers with interesting magnetic properties have been prepared based on [M(CN)8]3-,8 assembly of extended frameworks with [M(CN)8]3- instead of organic ligands still remains rare.9 In contrast to simple organic ligands, [M(CN)8]3- can adopt several different spatial configurations like polydentate “metalloligands”, which can give rise to extended solids with a variety of topological structures and

physical properties.10 On the basis of this route, a useful strategy for the assembly of heterobimetallic frameworks by employing inorganic linking unit [M(CN)8]3- is presented, although [M(CN)8]3- anions were reduced into diamagnetic [M(CN)8]4- during the reaction. We report herein two isomorphic novel 3D heterobimetallic MOFs {[μ4-M(CN)8]Cu2(DPP)4}n (M=W 1, Mo 2), constructed by [M(CN)8]4- and 2D {[Cu(DPP)2(SCN)2]}n nets,11 which were built by Cu atoms and DPP ligands, displaying a new topological geometry. The magnetic measurement of two MOFs shows typical paramagnetic properties and weak ferromagnetic interactions. Experimental Section

*Corresponding author. Fax: þ86-25-84318257 (C.Z.); þ81-52-789-2484 (K.A.). E-mail: [email protected] (C.Z.); [email protected]. nagoya-u.ac.jp (K.A.).

Materials and Methods. All reactions and manipulations were conducted in air except especially mentioned. The starting materials (Bu3N)3[W(CN)8] and (Bu3N)3[Mo(CN)8] were obtained according to the literature procedure.12 The solvents were roughly dried and distilled prior to use and other chemicals were generally used as commercially available. The elemental analysis for carbon, hydrogen and nitrogen were performed on a Perkin-Elmer 240C elemental analyzer. Infrared spectra were recorded with a Nicolet FT-170SX Fourier transform spectrometer (KBr pellets). Electronic spectra were measured on a Shimadzu UV-3100 spectrophotometer. Preparation of {[μ4-W(CN)8]Cu2(DPP)4}n 1. The reaction of CuSCN (0.248 g, 2 mmol) and NH4SCN (0.304 g, 4 mmol) with DPP (0.552 g, 4 mmol) in 10 mL DMSO solvent led to a light-yellow mixture. After stirring and filtration, 5 mL blank DMSO solvent and a solution of (Bu3N)3[W(CN)8] (1.118 g, 1.0 mmol) dissolved in 10 mL of methanol were successively layered on the top of the above filtrate carefully. MOF 1 was obtained as purple-red rhombus crystal after several days at room temperature. These crystals of 1 in a 18% yield based on Cu were collected by filtration, washed with ether and dried in air. Anal. Calcd for C60H56Cu2N16W (%): C, 54.87; H, 4.27; N, 17.07. Found: C 54.82; H 4.34; N 16.96. IR (KBr, cm-1): 2960w, 2183vs, 2129s, 1754vs, 1479s, 858s. Preparation of {[μ4-Mo(CN)8]Cu2(DPP)4}n 2. MOF 2 was obtained as purple rhombus crystal by a method similar to that

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of 1 except by using (Bu3N)3[Mo(CN)8] (1.028 g, 1.0 mmol) in stead of (Bu3N)3[W(CN)8] with a yield of 12%. Anal. Calcd for C60H56Cu2N16Mo (%): C, 58.87; H, 4.57; N, 18.30. Found: C, 58.81; H, 4.64; N, 17.93. IR (KBr, cm-1): 2960w, 2177vs, 2127s, 1743vs, 1463s, 835s. Single-Crystal Structure Determination. Suitable single crystals of dimensions 0.3  0.2  0.35 mm for 1 and 0.3  0.2  0.3 mm for 2 were selected and mounted in air onto thin glass fibers. The diffraction data were measured with Mo KR radiation (λ = 0.71070 A˚) 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. All structures were solved by direct methods and refined on F2 by full-matrix least-squares calculations with the using the SHELX-97 program package.13 All of the nonhydrogen atoms were refined with anisotropic thermal displacement coefficients. Hydrogen atoms of DPP were refined isotropically, all H-atoms were placed at calculated positions. Crystallographic data of MOFs 1 and 2 are summarized in the Table 1.

Results and Discussion Synthetic Procedure. As the direct addition of cyanometalates with various simple metal complexes always leads to Table 1. Crystal Data and Structure Refinements for MOFs 1 and 2 formula Mr T (K) cryst syst space group a (A˚) b (A˚) c (A˚) R (deg) β (deg) γ (deg) V (A˚3) Z Dcalcd (g cm-3) μ (mm-1) no. of reflns collected/unique R(int) GOF R1 (I > 2σ(I )) wR2 (I > 2σ(I )) ΔFmax (e A˚-3) ΔFmin (e A˚-3)

1

2

C60H56N16Cu2W 1312.15 223(2) tetragonal I 41/a 19.734(3) 19.734(3) 13.989(2) 90.00 90.00 90.00 5447.7(14) 4 1.600 2.937 2488/23363 0.0550 1.231 0.0403 0.0746 2.060 -0.987

C60H56N16Cu2Mo 1224.23 295(2) tetragonal I 41/a 19.7429(19) 19.7429(19) 13.9883(15) 90.00 90.00 90.00 5452.4(9) 4 1.491 1.056 2488/26318 0.0474 1.249 0.0520 0.0843 0.466 -0.446

the immediate precipitation due to the strong coordinating ability of the cyanide groups to many metal atoms, it is hard to get suitable single crystals for the structural determination and the physical measurements. Therefore, many wellshaped crystals of multidimensional polymers from octacyanometalates [M(CN)8]3- (M=W, Mo) and transition metals are obtained by the diffusion method.7f,8e,14 The preparation of MOFs 1 and 2, in this study, can be constructed as the interdiffusion approach in two steps: the first reaction of CuSCN and NH4SCN with the flexible bridging ligand DPP in solvent for building the 2D monometal Cu polymers, and the thereafter conformation of 3D MOF architectures with [M(CN)8]3- and 2D coordination networks by our developed interdiffusion method, as depicted in Scheme 1. On the basis of the molecular formula determined from the definitive crystal structures of MOFs 1 and 2, the most appropriate valences of Cu and M are 2þ and 4þ, respectively. It means that there might be a redox reaction during the synthetic process because the starting materials CuSCN and [M(CN)8]3- contain only the Cuþ and M5þ; while the valence of copper is changed from CuI to CuII by the reaction, the spin of the Cu will be varied from S=0 to S=1/2 with the M undergoing an opposite process from S = 1/2 (MV) to S = 0 (MIV). These spin numbers can explain the following magnetic properties well. Structural Analysis of MOFs 1 and 2. The X-ray singlecrystal structure analysis indicates that both 1 and 2 crystallize in the tetragonal space group I41/a, forming a 3D gridlike frame with several kinds of channels traversing the framework. The linking mode between Cu atom and [M(CN)8]4- unit reveals that Cu atoms and M atoms has a molar ratio of 1: 2 in the infinite 3D structures of MOFs 1 and 2. The structural study on MOFs 1 and 2 reveals a lacunaris framework, and the overall structure can be viewed as [M(CN)8]4- linking with 2D {[Cu(DPP)2(SCN)2]}n nets to create a consecutive 3D conformation. The connection between the Cu atoms and DPP ligands is extended to construct a 2D network structure, as shown in Figure 1a. From a topological viewpoint, each Cu atom adopts a fourconnected mode, and the structure of the 2D sheet can therefore be described as a sql (44) net.15 Attributed to the

Scheme 1. Preparation of the Title MOFs, {[μ4-M(CN)8]Cu2(DPP)4}n (M = W 1, Mo 2)

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Figure 1. (a) Infinite 2D layerlike structure linked by Cu atoms and DPP ligands; all hydrogen atoms were omitted for clarity (Cu red, C gray, N blue). (b) Impenetration of sheet by two vertical layers. (c) Schematic representation of the vertical layers which are linked by [M(CN)8]4(M = W, Mo) unit showing the polycatenated 3D structure (M green, Cu red).

flexibility of the DPP ligands, the void space of the single 2D network is so large that two identical nets can penetrate one sql net to form an unique 2D f 3D vertical polycatenated architecture (Figures 1b and 1c).16 The building unit [M(CN)8]4- is coordinated with four Cu atoms from four different sheets to construct the continuous 3D framework, as illustrated in Figure 1c. As shown in Figure 2, each M (M = W, Mo) atom is linked with the Cu atoms by μ-CN- bridges in a 4-connected mode forming a tetrahedron configuration, and the extended structure of this connection can be described as a foursquare fabric to enwrap the DPP ligands from the c axis. There are three kinds of channels arrayed in three layers within such a foursquare fabric, and each has four isomorphic channels in a same clockwise array, as displayed in Figure 2a. All the Cu atoms in these foursquare fabrics locate the middle of sides, while M atoms act as the nodes of the squares. Because of the tetrahedron configuration of the bridging [M(CN)8]4-, the linking between M and Cu atoms can not construct a single consecutive net in the direction of ab plane. The [M(CN)8]4- arraying along the c axis can also be represented as a string in the cavity of the 3D skeleton, which is formed by vertical 2D {[Cu(DPP)2(SCN)2]}n nets. In the 3D framework, there exists a 5-membered ring with two building blocks and three Cu atoms being alternately connected (see Figure S1 in the Supporting Information). The coordination environments for Cu and M atoms are displayed in Figure 2b. Selected parameters of MOFs 1 and 2 are listed in Table 2. The Cu atom is six-coordinated, having an octahedral geometry with four DPP ligands and two cis CNbridges. The bond distances between Cu atoms and N atoms from cis CN- bridges are 1.965(4) A˚ for 1 and 1.960(3) A˚ for 2, whereas the average values between Cu atoms and N atoms from DPP ligands are 2.276(4) A˚ for 1 and 2.271(3) A˚ for 2. Each [M(CN)8]4- is connected with Cu atoms by four μ-CNbridges while the remaining CN- groups are in the terminal position, forming a dodecahedron spatial configuration and exhibiting D2d symmetry. The bond lengths between M atoms and C atoms from μ-CN- bridges are 2.131(4) A˚ for 1 and 2.135(4) A˚ for 2, which are obviously shorter than the values 2.187(5) A˚ for 1 and 2.182(4) A˚ for 2 between M atom and C

Figure 2. (a) Packing diagram of 1 and 2 from the c axis, showing different channels through the framework. (b) The coordination mode of 1 and 2, showing the 4-connected [M(CN)8]4- units and the six-coordinated Cu atoms (M green, Cu red, C gray, N blue).

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Table 2. Selected Bond Length (A˚) and Selected Bond Angles (deg) of MOFs 1 and 2a MOF 1

MOF 2

W(1)-C(16) W(1)-C(16)#1 W(1)-C(16)#2 W(1)-C(16)#3 W(1)-C(15) W(1)-C(15)#1 W(1)-C(15)#2 W(1)-C(15)#3 Cu(1)-N(1) Cu(1)-N(3) Cu(1)-N(2) C(16)-W(1)-C(15) C(16)-W(1)-C(15)#3 C(16)#1-W(1)-C(16) C(16)#1-W(1)-C(16)#2 C(16)#1-W(1)-C(15) C(16)#1-W(1)-C(15)#3 C(16)#2-W(1)-C(15) C(16)#3-W(1)-C(15) N(1)-Cu(1)-N(2) N(1)-Cu(1)-N(2)#4 N(1)-Cu(1)-N(3)#4 N(1)#4-Cu(1)-N(1) N(1)#4-Cu(1)-N(3)#4 N(3)-Cu(1)-N(2)#4 N(3)#4-Cu(1)-N(3) N(3)#4-Cu(1)-N(2)#4

2.131(4) 2.131(4) 2.131(4) 2.131(4) 2.187(5) 2.187(5) 2.187(5) 2.187(5) 1.965(4) 2.113(4) 2.438(4) 75.98(16) 142.90(16) 146.3(2) 94.83(6) 76.87(16) 70.85(16) 142.90(16) 70.85(16) 90.11(14) 89.89(14) 89.46(15) 180.0(2) 90.54(15) 90.94(14) 180.0(3) 89.06(14)

Mo(1)-C(14)#2 Mo(1)-C(14)#1 Mo(1)-C(14) Mo(1)-C(14)#3 Mo(1)-C(15) Mo(1)-C(15)#3 Mo(1)-C(15)#1 Mo(1)-C(15)#2 Cu(1)-N(3) Cu(1)-N(1)#4 Cu(1)-N(2)#6 C(14)#2-Mo(1)-C(15) C(14)#2-Mo(1)-C(15)#2 C(14)#1-Mo(1)-C(14)#2 C(14)#1-Mo(1)-C(14) C(14)#1-Mo(1)-C(15) C(14)#1-Mo(1)-C(15)#2 C(14)-Mo(1)-C(15) C(14)#3-Mo(1)-C(15) N(3)-Cu(1)-N(2)#6 N(3)-Cu(1)-N(2)#5 N(3)-Cu(1)-N(1) N(3)#4-Cu(1)-N(3) N(3)#4-Cu(1)-N(1) N(1)#4-Cu(1)-N(2)#5 N(1)-Cu(1)-N(1)#4 N(1)-Cu(1)-N(2)#5

2.135(4) 2.135(4) 2.135(4) 2.135(4) 2.182(4) 2.182(4) 2.182(4) 2.182(4) 1.960(3) 2.110(3) 2.432(3) 70.73(13) 76.96(13) 146.60(18) 94.74(5) 142.66(13) 76.15(13) 76.96(13) 76.15(13) 89.80(12) 90.20(12) 90.39(12) 180.000(1) 89.61(12) 90.77(11) 180.0 89.23(11)

a Symmetry transformations used to generate equivalent atoms of MOF 1: #1: -x þ 0, -y - 1/2, z þ 0; #2: y þ 1/4, -x - 1/4, -z þ 3/4; #3: -y - 1/4, x - 1/4, -z þ 3/4; #4: -x - 1/2, -y - 1/2, -z þ 1/2; #5: -x - 1/2, -y - 1, z þ 1/2; #6: -x - 1/2, -y - 1, z - 1/2. Symmetry transformations used to generate equivalent atoms of MOF 2: #1: -y þ 5/4, x þ 1/4, -z þ 9/4; #2: y - 1/4, -x þ 5/4, -z þ 9/4; #3: -x þ 1, -y þ 3/2, z þ 0; #4: -x þ 1, -y þ 1, -z þ 2; #5: -x þ 3/2, -y þ 1, z þ 1/2; #6: x - 1/2, y, -z þ 3/2.

Figure 3. Topological segment of the new structure shows the detailed connection between the nodes and two kinds of edges (M in black, Cu in blue). -

atom from the remaining endmost CN groups, respectively. The C-M-C bond angles fall in the range 70.85(16)-146.3(2)° for 1 and 70.73(13)-146.60(18)° for 2. The network analysis reveals that 1 and 2 have a 2-nodal topological structure through assigning Cu and M atoms as two kinds of nodes, and the μ-CN- bridges and DPP ligands as the linkers (Figure 3). According to the determined crystal structure of MOFs 1 and 2, each M atom can be defined as a 4-connected node. Likewise, the 6-coordinated Cu atom connecting with four Cu atoms and two M atoms can accordingly act as a 6-connected node. In such a circumstance, the net of MOFs 1 and 2 represents a (4, 6)-connected topology. Vertex symbols for M node and Cu node are {54 3 62} and

Figure 4. χmT VS T plot for MOF 1.

{44 3 55 3 66}, respectively (see Figure S2 in the Supporting Information), and the molar ratio of M nodes and Cu nodes is 1:2, thus the point (Schl€ afli) symbol for this (4, 6)-connected net is {54 3 62} {44 3 55 3 66}2.17 Magnetic Properties. Temperature dependence measurements of molar magnetic susceptibility for MOFs 1 and 2 have been investigated under an applied field of 1000 G in the temperature range of 2-300 K, illustrating in Figure 4 in the form of χmT versus T. The curve shows a typical paramagnetic system with two spins of S = 1/2 and weak ferromagnetic interactions.18 The χmT value of 0.76 emu K mol-1 for 1 and 0.79 emu K mol-1 for 2 (see Figure S3 in the Supporting Information) at 300 K are almost consistent with the Curie value (spin-only moment value) of 0.75 emu K mol-1 for two

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isolated CuII (S = 1/2) ions, assuming g=2. As temperature is decreasing, χmT undergoes a gradual increase. This magnetic behavior indicates the existence of ferromagnetic interactions between magnetic centers. In the temperature range of 18-300 K, the inverse magnetic susceptibility data are fitted with the Curie-Weiss law, affording parameters of C = 0.74 emu K mol-1, θ = 1.3 K for 1, and C = 0.80 emu K mol-1, θ = 2.1 K for 2. The positive Weiss constants (θ) suggest that the magnetic interaction between the CuII through the diamagnetic -NC-MIV (S = 0)-CN- bridge exhibits weak ferromagnetic coupling. This coupling is induced by the spatial geometries such as the angle of Cu-M-Cu (M = W, Mo). Conclusions In summary, by applying the molecular building blocks [M(CN)8]3- as inorganic “metalloligands” with 2D {[Cu(DPP)2(SCN)2]}n nets, two novel 3D heterobimetallic assemblies with new topological structures have been constructed. The magnetic measurement of two MOFs shows typical paramagnetic properties and weak ferromagnetic interactions. Further studies of new functional heterobimetallic MOFs constructed by such a 2D f 3D synthetic strategy are currently in progress. Acknowledgment. Financial support from the National Natural Science Foundation of China for the Distinguished Young Scholar Fund to C.Z. (50925207), the Ministry of Science and Technology of China for the International Science Linkages Program (2009DFA50620), and the Special Fund for International Collaboration & Exchange of Jiangsu Province (BZ2008049) is acknowledged. K.A. and H.Y. are grateful to the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan for a Grant-inAid for Scientific Research. Supporting Information Available: Additional figures including topological cell, TOPOS results, and X-ray crystallographic information files (CIFs) are available for 1 and 2. CCDC 720894 and 722268. This information is available free of charge via the Internet at http://pubs.acs.org/.

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