Assembly of Multiply Chain-Modified Polyoxometalates: From One- to

Assembly of Multiply Chain-Modified Polyoxometalates: From Oneto Three-Dimensional and from Finite to Infinite Track Jingquan Sha,†,‡ Jun Peng,*,† Yu Zhang,‡ Haijun Pang,† Aixiang Tian,† Pengpeng Zhang,† and Hong Liu‡

CRYSTAL GROWTH & DESIGN 2009 VOL. 9, NO. 4 1708–1715

Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal UniVersity, Changchun, Jilin, 130024, P. R. China, and Faculty of Chemistry and Pharmacy, Jiamusi UniVersity, Jiamusi, HeilongJiang, 154007, P. R. China ReceiVed June 4, 2008; ReVised Manuscript ReceiVed December 31, 2008

ABSTRACT: By employing the polyoxometalates (POMs) with different sizes as structural motifs, three new organic-inorganic hybrids based on the multiply Cu-bipy coordination polymeric chain-modified POMs, [Cu(bipy)]2[HPMo12O40] (1), {[Cu(bipy)]4[GeW12O40]} · H2O (2), and {[Cu(bipy)]4[Mo15O47]} · 2H2O (3) (bipy ) 4,4′-bipyridine), have been hydrothermally synthesized and characterized by routine physical methods. Compound 1 exhibits 1D chain in which Keggin POMs are modified by bitrack Cu-bipy chains. Compound 2 represents a 2D layer of tetra-track Cu-bipy chain modified Keggin POMs. And compound 3 shows an infinitetrack Cu-bipy chain-modified molybdenum oxides 3D structure, namely, a modifying state of high point. Because the differences of POMs affect the structures of the hybridssthe number of Cu-bipy chains from bi- to infinite-track, and the dimension from 1D to 3Dstheir successful isolation demonstrates that members of the vast family of POMs may be employed as structural motifs in designing more solid-state materials. Additionally, their electrochemical properties have been studied. Introduction Explored early by Zubieta1 and You2 et al., the design and synthesis of organic-inorganic hybrid materials based on polyoxometalates (POMs) through crystal engineering have become a significant research area today for POM chemists because of their versatile architectures3 and potential applications in catalysis,4 photochemistry,5 electrochemistry,6 magnetism,7 and biochemistry.8 In recent years, a series of organic-inorganic hybrids made of POMs associated with various transition metal complexes (TMCs) have been reported,9 in which POMs as template/inorganic building blocks induce the self-assembly of the organic-inorganic hybrids. An acknowledged fact is that the assembly of POMs with TMC coordination polymers is a complicated process. However, only a few works have systemically illuminated the effect of some factors on the construction of POM-based hybrids, such as steric hindrance of the organic ligands, the size of POM anions, the pH of reaction system, and the nature of metal ions.10,11 In comparison with those of other hybrids, the rational design and assembly of hybrids based on POMs are more challenging because of the character of POMs. First, POMs exhibit a wide variety of structural motifs with different sizes and topologies, ranging from closed cages and spherical shells to basket-, bowl-, barrel- and belt-shaped structures.12 Second, POMs possess a large number of terminal and bridge oxygen atoms as potential active coordination sites to combine with TMCs, and the number of combined TMCs often is uncertain, depending on the nature of TMCs. Therefore, when POMs are used as modular inorganic building blocks, it is difficult to predict the primary selfassembly style in contrast to common metal complexes. Because POMs are a very important kind of inorganic species in hybrid solid materials, it is desirable to study systematically the roles of POMs in the assembly of the POM-based hybrids. We have successively obtained a series of multiply metal-N-chainmodified POMs by altering POMs in presence of rigid organic * Corresponding author. E-mail: [email protected] or [email protected]. † Northeast Normal University. ‡ Jiamusi University.

unit 4,4′-bipyridine (bipy).13-17 For the sake of comparison, their structural features are listed in Table 1. Although the formation mechanisms of these POM-based metal coordination polymers are not yet well understood, their structures are informative for understanding the roles of POMs. Their structural differences reveal the influence of POMs on the molecular assembly. It seems that the pendant modes of POM clusters in M-(bipy) chains determine the structural dimension and the number of M-bipy chains. The richer the pendant mode of the POM clusters is, the higher the structural dimension and the number of M-bipy chains are. However, we find that the highest number of metal-N chains that modify POM clusters is not more than seven to date, and it will have more space to extend the structural multiformity in face of the gigantic POM family. Resting on the aforementioned points, as a continuation of our research on the POM-based hybrid compounds, we select Keggin POMs (Mo- and W-systems) and molybdenum oxides as modular inorganic building blocks, 4, 4′-bipy ligands and Cu ions to build TMCs, in hopes of getting more information of POMs’ role in the assembly of extended structures of multiply Cu-bipy chain-modified POMs. Herein, we report three hybrid compounds, [Cu(bipy)]2[HPMo12O40] (1), {[Cu(bipy)]4[GeW12O40]} · H2O (2), and {[Cu(bipy)]4[Mo15O47]} · 2H2O (3), which exhibit chain, layer, and 3D frameworks, respectively. And the polyoxoanions are modified by bitrack chain for 1, tetratrack chain for 2, and infinite-track chain (a state of high-point) for 3. The influences of POMs on the dimensionality and the number of Cu-bipy chains are discussed. Experimental Section Materials and Methods. All reagents were purchased commercially and used without further purification except for the POMs. Elemental analyses (C, H, and N) were performed on a Perkin-Elmer 2400 CHN Elemental Analyzer, and on a Leaman inductively coupled plasma (ICP) spectrometer (Cu). The IR spectra were obtained on an Alpha Centaurt FT/IR spectrometer with KBr pellets in the 400-4000 cm-1 region. Cyclic voltammograms were obtained with a CHI 660 electrochemical workstation at room temperature. Platinum gauze was used as a counter

10.1021/cg800576b CCC: $40.75  2009 American Chemical Society Published on Web 02/27/2009

Assembly of Multiply Chain-Modified POMs

Crystal Growth & Design, Vol. 9, No. 4, 2009 1709

Table 1. Structural features of POMs in the POM-(M-bipy) (M ) Cu or Ag) Assemblies

§

* A, pendant modes of POM clusters in M-(bipy) chains: (a), up and down; (a’), up and down in pairs; (b), side by side; (c), between (a) and (b). B, structural dimension. ? C, the number of M-bipy chains.

electrode and Ag/AgCl electrode was referenced. Chemically bulkmodified carbon paste electrodes (CPEs) were used as working electrodes. Syntheses. [Cu(bipy)]2[HPMo12O40] (1). A mixture of H3[PMo12O40] (300 mg, 0.15mmol), Cu(NO3)2 · 3H2O (72 mg, 0.3mmol), 4,4′-bpy (57 mg, 0.3mmol), NH4VO3 (18 mg, 0.15mmol), triethylamine (trea) (1D), and H2O (10 mL) in a molar ratio 1:2:2:1:1:3500 was stirred for 1 h. The pH was then adjusted to 4.63 with 1 M NaOH, and the mixture was transferred to an 18 mL Teflon-lined reactor. After 6 days’ heating at 170 °C, the reactor was slowly cooled to room temperature over a period of 16 h. Brown like block crystals of 1 were filtered, washed with water, and dried at room temperature. Yield: 34% based on Cu. Calcd for C20N4H17Cu2PMo12O40 (2262.7): C, 10.61; H, 0.75; N, 2.47; Cu, 5.66. Found: C, 10.59; H, 0.84; N, 2.42; Cu, 5.64. {[Cu(bipy)]4[GeW12O40]} · H2O (2). Compound 2 was prepared in a manner similar to that described for 1, except the R-H4[GeW12O40] replaced the H3[PMo12O40]. The yield is 42% based on Cu. Calcd for C40H34N8Cu4GeW12O41 (3815.63): C, 12.58; H, 0.89; N, 2.94; Cu, 6.71. Found: C, 12.53; H, 0.93; N, 2.92; Cu, 6.65. {[Cu(bipy)]4[Mo15O47]} · 2H2O (3). A mixture of Na2MoO4 · 2H2O (145 mg, 0.6mmol), 4,4′-bpy (30 mg, 0.15mmol), Cu(NO3)2 · 3H2O (72 mg, 0.3mmol), NH4VO3(18 mg, 0.15mmol), and H2O (10 mL) in a molar ratio 4:1:2:1:3500 was stirred for 1 h. The pH was then adjusted to 4.5 with 1 M NaOH, and the mixture was transferred to an 18 mL Teflon-lined reactor. After 6 days’ heating at 170 °C, the reactor was slowly cooled to room temperature over a period of 16 h. Redlike block crystals of 3 were filtered, washed with water, and dried at room temperature. Yield: 25% based on Mo. Calcd for C40H36Cu4Mo15N8O49 (3106.03): C, 15.45; H, 1.15; N, 3.61; Cu, 8.24. Found: C, 15.41; H, 1.21; N, 3.56; Cu, 8.21. In the synthetic processes of compounds 1-3, the oxidation state of copper was changed from the reactant copper(II) to the resultant copper(I), which was confirmed by charge neutrality, coordination environments, and valence sum calculations. Such phenomena were often observed in the reaction of an N-containing ligand in the presence of copper(II) ion under hydrothermal conditions.18 Preparations of 1-, 2-, 3-CPEs. Compound 1-modified carbon paste electrode (1-CPE) was prepared as the following: 48 mg of graphite powder and 8 mg of compound 1 were mixed and ground together by agate mortar and pestle to achieve a uniform mixture, and then 0.6 mL

of nujol was added with stirring. The homogenized mixture was packed into a glass tube with 1.2 mm inner diameter, and the tube surface was wiped with paper. Electrical contact was established with copper rod through the back of the electrode. In a similar manner, 2- and 3- CPE electrodes were made with corresponding compounds 2 and 3. X-Ray Crystallographic Study. Crystal data for compounds 1-3 were collected on Rigaku RAXIS RAPID IP with Mo KR monochromatic radiation (λ ) 0.71073 Å) at 293/273 K. The structures were solved by the directed methods and refined by full matrix least-squares on F2 using the SHELXTL crystallographic software package.19 All the non-hydrogen atoms were refined anisotropically. The positions of hydrogen atoms on carbon atoms were calculated theoretically. Crystallographic data are given in Table 2.

Results and Discussion Structural Description of 1. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of one Keggin type [PMo12O40]3- (PMo12) anion, two Cu atoms, and two 4,4′-bipy molecules as shown in Figure 1a. Each Cu atom adopts a “seesaw” geometry coordinated by two nitrogen atoms of two 4,4′-bipy and two oxygen atoms of one PMo12 cluster. On one hand, PMo12 clusters acting as tetra-dentate inorganic ligands coordinate with two symmetrical CuI atoms through the bridging and terminal oxygen atoms (O9 and O20), and the bond distances of Cu-O are 2.688 Å (Cu1-O9) and 2.614 Å (Cu1-O20), whereas the O-Cu-O angle is 61.895°. On the other hand, each 4,4′-bipy ligand links two symmetrical CuI atoms into a Cu-bipy coordination polymeric chain. The bond distances of Cu-N are in the range of 1.886-1.901 Å, whereas the N-Cu-N angle is 174.45°. So that the CuI atoms fuse the chains and PMo12 clusters together to form 1D ladder-like chains, in which the PMo12 clusters are the “middle rails” of the ladder (shown in structures b and c in Figure 1). Furthermore, these 1D chains are linked via weak interactions to form a 2D structure (shown in Figure 2b).

1710 Crystal Growth & Design, Vol. 9, No. 4, 2009

Sha et al.

Table 2. Crystal Data and Structure Refinements for 1-3

a

compd

1

2

3

empirical formula formula weight CCDC T (K) wavelength (A°) cryst syst space group a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å3) Z Dcalc (mg/m3) absorp coeff (mm-1) F(000) GOF onF2 final R1 indicesa [I > 2σ(I)] final wR2 indicesb [I > 2σ(I)]

C20N4H17Cu2PMo12O40 2262.7 685310 293(2) 0.71073 triclinic P1j 10.861(2) 11.820(2) 13.243(3) 104.79(3) 102.91(3) 114.80(3) 1382.4 1 2.805 6.260 1080 1.079 0.0741 0.2143

C40H34N8Cu4GeW12O41 3815.63 685311 273(2) 0.71073 triclinic P1j 14.383(4) 14.400(4) 21.420(5) 96.724(5) 96.541(5) 109.438(4) 4099.1 2 5.000 34.194 5338 1.010 0.0915 0.2289

C40H36Cu4Mo15N8O49 3106.03 685312 273(2) 0.71073 monoclinic C2/c 27.2772(1) 3.7627(3) 21.8196(1) 90 122.034(2) 90 1898.5 4 2.834 6.948 1488 1.032 0.0829 0.2378

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

Figure 1. (a) Structure drawing of the fundamental building block of compound 1. The hydrogen atoms are omitted for clarity. (b) The ladderlike chain with PMo12 clusters as “middle rails” in compound 1. (c) Schematic view of the bitrack Cu(bipy) chain-modified POMs.

Figure 2. (a) Combined polyhedral/wire representation and (b) schematic view of 2D supramolecular structure in 1 along the given directions.

Structural Description of 2. Single-crystal X-ray diffraction analysis reveals that compound 2 consists of one Keggin type [GeW12O40]3- (GeW12) anion, four Cu atoms, four 4,4′-bipy molecules, and one water molecule as shown in Figure 3. Note that there are four independent Cu(I) centers, in which Cu1 and

Cu2 are tetra-coordinated by two nitrogen atoms of two 4,4′bipy and two oxygen atoms (terminal and bridge oxygen) of one GeW12 anion; Cu3 and Cu4 are tricoordinated by two nitrogen atoms of two 4,4′-bipy and one terminal oxygen atom of GeW12 anion. The Cu-O bond distances are in the range of



Figure 3. Structure drawing of the fundamental building block of compound 2. The hydrogen atoms and crystal water molecules are omitted for clarity.

Figure 4. (a) Stick representation of 2D layer structure in 2. (b) Schematic view of the tetra-track Cu(bipy) chains modified POMs.

2.196-2.834 Å, and the bond angles of N-Cu-N are in the range of 154.7-168.2°, and N-Cu-O in the range of 91.8-107.3°. Different from compound 1, each 4,4′-bpy ligand links two asymmetrical Cu(I) atoms into 1D Cu1(3)-bipy-Cu2(4) chain, and the GeW12 anion as a hexad-dentate inorganic ligand coordinates with four Cu centers (the insert of Figure 3). In comparison with that of compound 1, the linking mode between POM and Cu is changed, namely, each pair of adjacent GeW12 clusters covalently bonds to four Cu(I) centers from opposite directions. Thus the two adjacent POM clusters (including bonded Cu) present an inversed relation. Owing to POM groups with two opposite directions along the a axis and the inversed subunits arraying alternately in the two sides of each pair of chains along the c axis direction, a 2D layer is extended on the [010] plane, in which POM clusters and Cubipy chains are alternatively arranged to form a net and generate big vacancies (ca. 27.4 × 11.9Å) (Figure 4a). As a result, the 2D layer of tetra-track Cu-bipy chain-modified Keggin POM is formed (Figure 4b). However, 2D layers are stacked to 3D framework in parallel staggering fashion, making the pores disappeared, as shown in Figure 5. Selected bond lengths and angles for 2 are collected in Table S2 of the Supporting Information. Structural Description of 3. Single-crystal X-ray diffraction analysis reveals that compound 3 consists of one molybdenum oxide cluster, four [Cu(bipy)]+ cations, and two water molecules (shown in Figure 6a). As shown in Figure 6b, in the molybdenum oxides, there are two distinct Mo environments. The Mo1

Figure 5. Schematic representation of 3D network in 2.

atoms have two terminal, one doubly bridging, and three triply oxygen atoms and form Mo1 chain via corner-sharing octahedra. Each Mo2 site has a single terminal, one doubly bridging, and four triply bridging oxo groups and form a double-chain via planar, edge-sharing octahedra. Furthermore, the double-chain of Mo2 centers links two Mo1 chains, resulting in the [Mo15O47]n4n- chains, whose structure is the same as that of [Mo15O47]n4n- chains reported by Zubieta.20 Similar to compound 1, each 4,4′-bipy ligand links two symmetrical CuI atoms into a Cu-bipy coordination polymeric chain. And the terminal oxygen atom (O5) of each Mol center coordinates to Cu(I) atom(shown in Figure 7a), resulting in an infinite-track Cu-bipy chain-modifyed molybdenum oxide chain (shown in Figure 7b). Note that the compound 3 represents a state of high-point about multitrack Cu-N coordination polymeric chain-modifyed POMs.


Sha et al.

Figure 6. (a) Structure drawing of the fundamental building block of compound 3. The hydrogen atoms and crystal water molecules are omitted for clarity. (b) Ball/stick representation of [Mo15O47]n4n- chain structure.

Figure 7. (a) Combined polyhedral/stick representation of 2D layer in compound 3. (b) Schematic view of the infinite-track Cu(bipy) chainmodified POM 3.

Influence of Polyoxoanion on the Structures of Multiply Cu-bipy Coordination Polymeric Chain-modified POMs. In this work, through changing the POM clusters, we have achieved the alternation of dimensionality and the number of Cu-N chains to observe the effect of POM clusters on the POM-based Cu-bipy assembly. Compounds 1 and 2 were synthesized under identical reaction conditions except for the alternation of Keggin POMs, but the final structures are distinctly different, which rests on the differing volumes and oxygen basicities of the Keggin POMs. In compound 1, PMo12 clusters act as tetradentate chelate inorganic ligands to coordinate to the Cu centers of the Cu-N chains, generating an interesting ladderlike chain, in which PMo12 clusters (ca.10.36 Å) are small enough to array in a “side-by-side” way. This linking mode stops highly connecting of the POMs with Cu-bipy complexes. However, in compound 2, the GeW12 clusters act as hexad-dentate chelate and terminal inorganic ligands to coordinate to Cu centers of the Cu-bipy chains, forming a 2D grid net, and the rigid Cubipy chains no longer accommodate the bigger GeW12 cluster (ca.10.45Å) “side-by-side”; instead, GeW12 clusters array in pairs in an “up and down” mode. This linking mode favors the extension of the structure. In compound 3, because of the polymerization of molybdenum oxide, the Mo4O12 subunit is extended to a 1D chain, which makes multiply modifying of the POM cluster by Cu-bipy chains more easy. The small Mo4O12 subunit acts as a bidentate bridging inorganic ligand to coordinate to Cu centers of the Cu-bipy chains, generating an interesting grid layer, in which the Mo4O12 subunits array in a mixed way of the “side-by-side” and “up and down” modes. Furthermore, the molybdenum oxide chain acting as an infinite-

dentate inorganic ligand to coordinate to the Cu centers results in an infinite-track Cu-bipy chain-modified POMs. The bond valence sum calculations (BVS)21 indicate that all copper atoms are in the +1 oxidation state, while all molybdenum and tungsten atoms are in +6 oxidation state in compounds 1-3. Similar to the case of [Ag2(3atrz)2]2[(HPMoVI10MoV2O40)],22 to balance the charge of the compound, a proton is added, and 1 is then formulated as [Cu(bipy)]2[HPMo12O40]. FT-IR Spectra. In the IR spectra (see Figure S1 in the Supporting Information), characteristic peaks at 1056, 950, 869, 802 cm-1 for compound 1 are attributed to νas(P-O) νas(Mo-Od), νas(Mo-Ob-Mo), and νas(Mo-Oc-Mo) vibrations, which are nearly identical to those of [PMo12O40]3- except for slight changes in peak position perhaps due to the coordination. For compound 2, characteristic peaks at 944, 863, and 773 cm-1 are attributed to νas(W-Od), νas(W-Ob-W), and νas(W-Oc-W) of [GeW12O40]4- polyoxoanion, respectively. In the IR spectrum of compound 3, characteristic peaks at 965, 895, and 446 cm-1 are attributed to ν(Mo-Od) and ν(W-Ob/c-W) of [Mo15O47]n4npolyoxoanion, respectively. Furthermore, a series of characteristic bands in the 1380-1700 cm-1 region are associated with 4,4′-bipy groups in 1-3. Cyclic Voltammetric Behaviors of 1-, 2-, and 3-CPE in Aqueous Electrolyte. To study the redox properties of compounds 1-3, we use them as modifiers to fabricate chemically modified CPEs, because of their insoluble in water and most organic solvents. In the potential range, we explored their typical cyclic voltammetric behavior of CPEs in 1 mol L-1 H2SO4



Figure 8. Cyclic voltammograms of the 1-, 2-, and 3-CPE in 1 M H2SO4 at the different scan rates (from inner to outer: 30, 60, 90, 120, 150, 180, 210, 240, 270, and 300 mV s1-).

Figure 9. Cyclic voltammograms of 1-, 2-, and 3-CPE in 1 M H2SO4 containing (a) 0, (b) 4, (c) 8, and (d) 12 mM NaNO2 (scan rate 90 mV s -1).

aqueous solution at different scan rates. As shown in Figure 8, in the given potential range, three pairs of reversible redox peaks (I-I′, II-II′, III-III′) appear and the mean peak potentials E1/2

) (Epc + Epa)/2 are +22, +240, +381 mV for 1, +253, +387, +466 mV for 3 (30 mV/s), respectively, showing three continuous two-electron process of Mo atoms. Two pairs of


reversible redox peaks (I-I′, II-II′) appear for 2 and the mean peak potentials E1/2 are -562 and -410 mV, respectively, corresponding to two one-electron redox processes of W atoms, and the third (III) irreversible anodic peak is assigned to the oxidation of Cu(I) (E ) 191 mV). With the scan rate increasing, the peak potentials change gradually: the cathodic peak potentials shifted to the negative direction and the corresponding anodic peak potentials to the positive direction, namely, the peak-to-peak separation between the corresponding cathodic and anodic peaks increased, but the mean peak potentials did not change on the whole. Electrocatalytic Activity of 1-, 2-, and 3-CPE for the Reduction of Nitrite. As is known, POMs have been exploited extensively in electrocatalytic reductions. For example, Dong, Keita, Toth and their co-workers have used Keggin POMs as electrocatalyst for the reduction of nitrite and hydrogen peroxide.23 Herein, compounds 1-3 are employed to fabricate POMmodified electrodes to catalyze the reduction of nitrite. Because of the high overpotential required at most electrode surfaces for direct electroreduction of nitrite ion, no obvious response is observed for nitrite at bare CPE in the potential range. Figure 9 shows the cyclic voltammograms of 1-CPE to 3-CPE under scan rate 90 mV s -1 in an acid solution containing nitrite. The result indicates that CPEs have good electrocatalytic activities for the reduction of nitrite. For the 1-CPE and 3-CPE, with the addition of nitrite, all t three reduction peak currents increase markedly while the corresponding oxidation peak currents decrease, suggesting that the reduction of nitrite involves the two-, four-, and six- electron reduced species. It has been noted that the six-electron reduce species has the largest catalytic activity toward the reduction of nitrite. And for the 2-CPE, all the two reduction peak currents also increase markedly while the corresponding oxidation peak currents decrease, suggesting that the reduction of nitrite involves the one- and two-electron-reduced species of the POM. The results indicate that the CPEs have a good electrocatalytic activity for the reduction of nitrite. Conclusion On the basis of our pervious work, we investigate systematically the effect of POMs on the structures of the rigid M-bipy chain-modified POMs by changing the POMs, and three new multiply Cu-bipy coordination polymeric chain-modified POMs have been successfully obtained, in which compound 3 exhibits a state of high-point of the multiply modifying of the Cu-bipy chains. The three compounds show again the different volumes and basicities of the POMs can influence the dimension of the hybrid materials and the number of coparallel multichains of the Cu-bipy coordination polymer. This work proves again the potential of reasonable design and controllable assembly of POM-based hybrid compounds. Acknowledgment. This work is financially supported by the National Natural Science Foundation of China (20671016), the Program for Changjiang Scholars and Innovative Research Team in University, Education Office Foundation of the Heilongjiang Province 11531379. Supporting Information Available: Tables of selected bond lengths (Å), bond angles (deg) and IR for compounds 1-3. This material is available free of charge via the Internet at http://pubs.acs.org.

References (1) Hagrman, D.; Zubieta, C.; Rose, D. J.; Zubieta, J.; Haushalter, R. C. Angew. Chem., Int. Ed. 1997, 36, 873–875.

Sha et al. (2) Xu, Y.; Xu, J. Q.; Zhang, K. L.; Zhang, Y.; You, X. Z. Chem. Commun. 2000, 6, 153–154. (3) (a) Pope, M. T. Heteropoly and Isopoly Oxometalates; Springer-Verlag: New York, 1983. (b) Pope, M. T., Mu¨ller, A., Eds. Polyoxometalate Chemistry from Topology Via Self-Assembly to Applications; Kluwer Academic Publishers: Dordrecht, The Netherlands, 2001. (4) (a) Mu¨ller, A.; Pope, M. T.; Peters, F.; Gatteschi, D. Chem. ReV. 1998, 98, 239–272. (b) Artero, V.; Proust, A.; Herson, P.; Villain, F.; Moulin, C.; Gouzerh, P. J. Am. Chem. Soc. 2003, 125, 11156–11157. (5) (a) Ko¨gerler, P.; Cronin, L. Angew. Chem., Int. Ed. 2005, 44, 844– 846. (b) Yamase, T. J. Chem. Soc., Dalton Trans. 1985, 2585, 2590. (6) Coronado, E.; Galań-Mascaro´s, J. R.; Gimeńez-Saiz, C.; Go´mezGarcıá, C. J.; Martıńez-Ferrero, E.; Almeida, M.; Lopes, E. B. AdV. Mater. 2004, 16, 324–327. (7) (a) Pope, M. T.; Mu¨ller, A. Angew. Chem., Int. Ed. 1991, 30, 34–48. (b) Mu¨ller, A. Nature 1991, 352, 115. (c) Coronado, E.; Go´mez-Garcıá, C. J. Chem. ReV. 1998, 98, 273–296. (d) Lisnard, L.; Mialane, P.; Dolbecq, A.; Marrot, J.; Clemente-Juan, J. M.; Coronado, E.; Keita, B.; Oliveira, P.; Nadjo, L.; Secheresse, F. Chem.sEur. J. 2007, 13, 3525–3536. (8) (a) Rhule, J. T.; Hill, C. L.; Judd, D. A. Chem. ReV. 1998, 98, 327– 358. (b) Wang, X.; Liu, J.; Pope, M. Dalton Trans. 2003, 957, 960. (9) (a) Wang, X. L.; Qin, C.; Wang, E. B.; Su, Z. M.; Li, Y. G.; Xu, L. Angew. Chem., Int. Ed. 2006, 45, 7411–7414. (b) An, H. Y.; Xiao, D. R.; Wang, E. B.; Li, Y. G.; Su, Z. M.; Xu, L. Angew. Chem., Int. Ed. 2006, 45, 904–908. (c) Zheng, S. T.; Wang, M. H.; Yang, G. Y. Inorg. Chem. 2007, 46, 9503–9508. (d) Streb, C.; Ritchie, C.; Long, D. L.; Ko¨gerler, P.; Cronin, L. Angew. Chem., Int. Ed 2007, 46, 1–5. (e) Wei, M. L.; He, C.; Sun, Q. Z.; Meng, Q. J.; Duan, C. Y. Inorg. Chem. 2007, 46, 5957–5966. (f) Ritchie, C.; Burkholder, E.; Ko¨gerler, P.; Cronin, L. Dalton Trans. 2006, 1712–1714. (10) (a) Dong, B. X.; Peng, J.; Gomez-Garcia, C. J.; Benmansour, S.; Jia, H. Q.; Hu, N. H. Inorg. Chem. 2007, 46, 5933–5941. (b) Ren, Y. P.; Kong, X. J.; Hu, X. Y.; Sun, M.; Long, L. S. Inorg. Chem. 2006, 45, 4016–4024. (c) Ren, Y. P.; Kong, X. J.; Long, L. S.; Huang, R. B.; Zheng, L. S. Cryst Growth Des 2006, 6, 572–576. (d) Kong, X. J.; Ren, Y. P.; Zheng, P. Q.; Long, Y. X.; Long, L. S.; Huang, R. B.; Zheng, L. S. Inorg. Chem. 2006, 45, 10702–10711. (e) Zheng, P. Q.; Ren, Y. P.; Long, L. S.; Huang, R. B.; Zheng, L. S. Inorg. Chem. 2005, 44, 1190–1192. (11) (a) Soghomonian, V.; Chen, Q.; Haushalter, R. C.; Zubieta, J.; OConnor, J. C. J.; Leelc, Y. S. Chem. Mater. 1993, 5, 1690–1691. (b) LaDuca, Jr. R. L.; Rarig, Jr. R. S.; Zubieta, J. Inorg. Chem. 2001, 40, 607–612. (c) Hagrman, P. J.; Zubieta, J. Inorg. Chem. 2001, 40, 2800–2809. (d) Pamela, Z. J.; Robert, L. Jr.; Randy, Jr. S. R.; Kenneth, M. J.; Zubieta, J. Inorg. Chem. 1998, 37, 3411–3414. (e) Hagrman, P. J.; LaDuca, Jr. R.L.; Koo, H. J.; Rarig, Jr. R.; Haushalter, R. C.; Whangbo, M. H.; Zubieta, J. Inorg. Chem. 2000, 39, 4311–4317. (f) Hagrman, P. J.; Zubieta, J. Inorg. Chem. 2000, 39, 5218–5224. (g) Shi, Z. Y.; Peng, J.; Gomez-Garcia, C. J.; Benmansour, S.; Gu, X. J. Solid State Chem. 2006, 179, 253–265. (12) (a) Klemperer, W. G.; Marquart, T. A.; Yagi, O. M. Angew. Chem., Int. Ed. 1992, 31, 49–51. (b) Klemperer, W. G.; Marquart, T. A.; Yagi, O. M. Angew. Chem. 1992, 104, 51–53. (c) Day, V. W.; Klemperer, W. G.; Yagi, O. M. J. Am. Chem. Soc. 1989, 111, 5959–5961. (d) Johnson, G. K.; Schlemper, E. O. J. Am. Chem. Soc. 1978, 100, 3645– 3646. (e) Chen, L.; Jiang, F. L.; Lin, Z Z.; Zhou, Y. F.; Yue, C. Y.; Hong, M. C. J. Am. Chem. Soc. 2005, 127, 8588–8589. (f) Khan, M. I.; Zubieta, J. Angew. Chem., Int. Ed. 1994, 33, 760–762. (g) Salta, J.; Chen, Q.; Chang, Y. D.; Zubieta, J. Angew. Chem., Int. Ed. 1994, 33, 757–760. (13) Sha, J. Q.; Peng, J.; Liu, H. S.; Chen, J.; Dong, B. X.; Tian, A. X.; Su, Z. M. Eur. J. Inorg. Chem. 2007, 46, 11183–11189. (14) Sha, J. Q.; Peng, J.; Tian, A. X.; Liu, H. S.; Chen, J.; Zhang, P. P.; Su, Z. M. Cryst. Growth Des. 2007, 7, 2535–2541. (15) Sha, J. Q.; Wang, C.; Peng, J.; Chen, J.; Tian, A. X.; Zhang, P. P. Inorg. Chem. Commun. 2007, 10, 321–1324. (16) Sha, J. Q.; Peng, J.; Lan, Y. Q.; Su, Z. M.; Pang, H. J.; Tian, A. X.; Zhang, P. P.; Zhu, M. Inorg. Chem. 2008, 47, 5154–5153. (17) Sha, J. Q.; Peng, J.; Lan, Y. Q.; Su, Z. M.; Pang, H. J.; Tian, A. X.; Zhang, P. P.; Zhu, M. Inorg. Chem. 2008, 47, 5145–5153. (18) (a) Wang, X. L.; Qin, C.; Wang, E. B.; Su, Z. M. Chem. Commum. 2007, 4245–4247. (b) Tian, A. X.; Ying, J.; Peng, J.; Sha, J. Q.; Han, Z. G.; Ma, J. F.; Su, Z. M.; Hu, N. H.; Jia, H. Q. Inorg. Chem. 2005, 47, 3278–3238. (19) (a) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure Solution; University of Go¨ttingen: Go¨ttingen, Germany, 1997. (b) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure Refinement; University of Go¨ttingen: Go¨ttingen, Germany, 1997.

Assembly of Multiply Chain-Modified POMs (20) Hagrman, D.; Zubieta, C.; Rose, D. J.; Zubieta, J.; Haushalter, R. C. Angew.Chem., Int. Ed. 1997, 36, 873–876. (21) Brown, I. D.; Altermatt, D. Acta Crystallogr., Sect. B 1985, 41, 244. (22) Zhai, Q. G.; Wu, X. Y.; Chen, S. M.; Zhao, Z. G.; Lu, C. Z. Inorg. Chem. 2007, 46, 5046–5058.

Crystal Growth & Design, Vol. 9, No. 4, 2009 1715 (23) (a) Keita, B.; Belhouari, A.; Nadjo, L.; Contant, R. J. Electroanal. Chem. 1995, 381, 243–250. (b) Toth, J. E.; Anson, F. C. J. Electroanal. Chem. 1988, 256, 361–370.

CG800576B

Assembly of Multiply Chain-Modified Polyoxometalates: From One- to

Recommend Documents