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A novel bismuth ion-bridged chainlike assembly from paradodecatungstate [H2W12O42]10− anions: (NH4)7[Bi(H2W12O42)] · 20H2O
Inorganic Chemistry Communications 10 (2007) 276–278 www.elsevier.com/locate/inoche
A novel bismuth ion-bridged chainlike assembly from paradodecatungstate [H2W12O42]10 anions: (NH4)7[Bi(H2W12O42)] Æ 20H2O Zhen-He Xu, Xin-Long Wang, Yang-Guang Li, En-Bo Wang *, Chao Qin, Yan-Ling Si Key Laboratory of Polyoxometalate Science of Ministry of Education, Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun Jilin 130024, People’s Republic of China Received 30 September 2006; accepted 7 November 2006 Available online 16 November 2006
Abstract A new polyoxotungstate (NH4)7[Bi(H2W12O42)] Æ 20H2O has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, TG analysis and single-crystal X-ray diffraction. The most interesting structural feature of 1 is that the paradodecatungstate [H2W12O42]10 anions are linked, for the first time, by the trivalent main group atom BiIII which appeared commonly as a heteroatom in polyoxometalate chemistry, into a one-dimensional chainlike structure. Ó 2006 Elsevier B.V. All rights reserved. keywords: Polyoxometalates; Crystal structure; Bismuth; Tungstate
Polyoxometalates (POMs), as one kind of significant metal oxide cluster with nanosizes and abundant topologies, have been attracting extensive interest in fields such as catalysis, electrochemistry, electrochromism and magnetism [1]. The evolution of polyoxometalate chemistry is dependent upon the synthesis of new solids possessing unique structures and properties. Although synthesis of the materials remains a challenge, a large number of novel polyoxoanions with unexpected shapes and sizes are still being discovered [2]. Therefore, the self–assembly process of nanoscale polyoxometalates has attracted the attentions of many groups, and a series of the novel POMs possessing unique structure and properties have been reported [3]. It is noteworthy that one of the intriguing fields in the polyoxometalate chemistry is to find some novel subunits and then connect them into one-, two-, even three-dimensional (1D, 2D, even 3D) extended networks, either through direct condensation to form oxo-bridged arrays *
Corresponding author. Tel./fax: +86 431 5098787. E-mail addresses: [email protected], wangenb889@nenu. edu.cn (E.-B. Wang). 1387-7003/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2006.11.004
of clusters or through transition metal coordination complexes acting as inorganic bridging ligands [4]. To date, the commonly used polyoxometalate building blocks are still limited to well-known Keggin- [5], Wells–Dawson[6], Anderson- [7], Silverton- [8], and Lindquist-type [9] anions et al., and furthermore, the most extended frameworks based on these polyanions are achieved via the bridges of metal-organic complexes [10]. In contrast, bridging suitable metal oxide building blocks by simple linking units to generate true metal oxide surfaces and framework materials without the incorporation of additional conventional ligands still remains largely unexplored [11]. This kind of material is usually stable and insoluble in common organic solvent, whose property is very advantageous to expand application of POM–based materials in chemically bulk–modified electrode [12]. Among the various types of polyanions, the paradodecatungstate anion [H2W12O42]10 possesses some particular structural features, and provides a variety of possibilities of intermolecular linkages [13]. However, examples utilizing of this anion for the design and synthesis of POMs with extended structures are rarely reported. On
Z.-H. Xu et al. / Inorganic Chemistry Communications 10 (2007) 276–278
the other hand, as we know, the trivalent main group atom BiIII, similar to the PV and AsV atoms of the same main group, is exclusively act as heteroatom in the reported POM compounds [14]. Up to now no cases have been observed in which bismuth atom serve as a linker to assist the self-assembly of POM building blocks. Fortunately, here we reported a one-dimensional chainlike compound (NH4)7[Bi(H2W12O42)] Æ 20H2O 1 that is formed, for the first time, by linking [H2W12O42]10 clusters with Bi atoms. To our knowledge, 1 represents the first characterized POM compound containing Bi atoms as bridges. The title compound was synthesized from aqueous media and isolated as colorless columnar crystals [15]. Single-crystal X-ray diffraction analysis [16] shows that compound 1 exhibits a novel 1D structure built from paradodecatungstate [H2W12O42]10 units linked by Bi cation to yield a polymeric chain. The paratungstate–B units is structurally identical to those reported previously, e.g. K6[Co(H2O)4]2 Æ [H2W12O42] Æ 14H2O, Na2[H2W12O42] Æ 20H2O, Mg5[H2W12O42] Æ 38H2O [13]. As shown in Fig. 1, this polyoxoanion is centrosymmetric and consists of four corner–sharing groups of two types, each type containing three edge-sharing WO6 octahedra. All tungstate sites exhibit +VI oxidation state, possessing octahedral coordination geometry with different distortion extents. The +VI oxidation state is also confirmed by bond valence sum calculations [17], which gives the values of 6.204(44), 6.417(05), 5.894(79), 5.926(24), 6.003(04) and 5.975(81) for W(1), W(2), W(3), W(4), W(5) and W(6). The average value for the calculated oxidation states of W is 6.070(22), showing that all W sites are in the +6 oxidation state. This result is consistent with the formula of the title compound given by X-ray structure determination. The W–O bonds can be divided into four groups: (i) tung˚ ; (ii) tungsten–terminal oxygen, 1.708(15)–1.734(15) A sten–oxygen linked to bismuth atom, 2.348(13)–2.525(16) ˚ ; (iii) tungsten–bridging oxygen, 1.770(14)–2.229(16) A ˚; A (iv) tungsten–internal oxygen common to three tungsten ˚ . These results shows that atoms, 1.900(14)–2.2501(13) A WO6 octahedra of anions are severely distorted, indicating that the strong interaction between the polyanions and Bi cations. In compound 1, the [H2W12O42]10 cluster acts as tetradentate ligands coordinating to two Bi ions through terminal oxygen atoms of four WO6 belonging to the belt–
Fig. 1. Combined polyhedral/ball-and-stick representation of 1. The purple octahedra represent WO6 and the balls represent Bi (cyan) and O (red). (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
277
Fig. 2. Polyhedral representation of the 1D ‘‘zig-zag’’ chain in 1.
type W3O14 groups (Fig. 2). The coordination site of the bismuth ions might be described as a distorted pseudotrigonal bipyramid BiO4X with the lone pair X occupying an axial position, and the bismuth–oxygen distances are ˚ and the angles of in the range of 2.346(12)–2.518(15) A Bi–O–Bi are in the range of 78.9(4)–153.3(6)°. Compared with all known extended structures based on [H2W12O42]10 anion in which adjacent anions are connected by transition metal ions, compound 1 represents the first characterized paradodecatungstate containing the fifth main group element as bridges. In the IR spectrum of the title compound, the characteristic bands at 958, 899, 656, 588, 564, and 481 cm1are attributed to the W = O and W–O–W vibrations. Comparing the IR spectrum of compound 1 with that of [H2W12O42]10 [13], it can be observed that the shape of the peaks in the range 400–1000 cm1 is nearly identical to that of [H2W12O42]10 except slight shifts of some peaks due to the effect of coordination, which indicates that the polyanion in the title compound still retains the basic [H2W12O42]10 structure. This is in agreement with the result of single-crystal X-ray diffraction analysis. The IR spectrum studies indicate that there is strong interaction between the polyanions and bismuth ions in solid state. Thermogravimetric analysis of compound 1 shows four weight loss steps in the range of 40–770 °C (Fig. 3), corresponding to the release of all crystalline water molecules, and the NH3 molecules derived from the decomposition of NHþ 4 ions as well as the H2O water molecule forms derived from the combination of H and O atoms in the compound, respectively. The total weight loss of 14.13%
Fig. 3. The TG curve of compound 1.
278
Z.-H. Xu et al. / Inorganic Chemistry Communications 10 (2007) 276–278
agrees with the calculated value of 14.18%. It can be observed that the result of the TG analysis agrees with that of the structure determination. In summary, we have reported a novel chain-like extended structure based on paradodecatungstate polyanion and Bi cation linker. The synthesis of compound 1 from well-defined discrete building blocks indicates that the diversity of pathways using metastable precursors to synthesize novel structures and species. Under similar conditions, some extended experiments can be done: it is possible to incorporate many other electrophiles, e.g. rare earths, and many possible novel species are very likely to be obtained. Now, we are exploring this avenue.
[6]
[7]
[8] [9]
Acknowledgement [10]
This work was supported by the National Science Foundation of China (No. 20371011). Appendix A. Supplementary materials Crystal data and structure refinement, atomic coordinates, bond lengths and angles, anisotropic displacement parameters, and IR spectra of compound 1 was available from the authors on request. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2006.11.004.
[11]
[12]
References [13] [1] (a) M.T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin, 1983; (b) J.S. Anderson, Nature 140 (1937) 850; (c) C.L. Hill, Chem. Rev. 98 (1998) 1; (d) B.B. Xu, Z.H. Peng, Y.G. Wei, D.R. Powell, Chem. Commun. (2003) 2562; (e) L.C. Baker, D.C. Glick, Chem. Rev. 98 (1998) 3. [2] (a) R.C. Howell, F.G. Perez, S. Jain, W.D. Horrocks, J.A.L. Rheingold, L.C. Francesconi, Angew. Chem. Int. Ed. 40 (2001) 4031; (b) P. Mialane, A. Dolbecq, J. Marrot, E. Rivie`re, F. Se´cheresse, Chem. Eur. J. 11 (2005) 1771; (c) S. Reinoso, P. Vitoria, L.S. Felices, L. Lezama, J.M. Gutie´rrezZorrilla, Chem. Eur. J. 11 (2005) 1538; (d) S.T. Zheng, J. Zhang, G.Y. Yang, Inorg. Chem. 44 (2005) 2426; (e) J.Y. Niu, D.J. Guo, J.P. Wang, J.W. Zhao, Cryst. Growth Des. 4 (2004) 241. [3] (a) Y. Xia, P.F. Wu, Y.G. Wei, Y . Wang, H.Y. Guo, Cryst. Growth Des. 6 (2006) 253; (b) X.B. Cui, J.Q. Xu, H. Meng, S.T. Zheng, G.Y. Yang, Inorg. Chem. 43 (2004) 8005; (c) J.Y. Niu, Q. Wu, J.P. Wang, J. Chem. Soc., Dalton Trans. (2002) 2512. [4] B. Yan, Y. Xu, X. Bu, N.K. Goh, L.S. Chia, G.D. Stucky, J. Chem. Soc. Dalton Trans. (2001) 2009–2014. [5] (a) M. Sadakane, M.H. Dickman, M.T. Pope, Angew. Chem., Int. Ed. 39 (2000) 2914; (b) J.M. Galan-Mascaros, C. Gimenez-Saiz, S. Triki, C.J. GomezGarcia, E. Coronado, L. Ouahab, Angew. Chem., Int. Ed. Engl. 34 (1995) 1460;
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(c) A. Mu¨ller, M. Koop, P. Schiffels, H. Bo¨gge, Chem. Commun. (1997) 1715. (a) J.Y. Niu, D.J. Guo, J.P. Wang, J.W. Zhao, Cryst. Growth. Des. 5 (2005) 1837–1843; (b) Y. Lu, Y. Xu, Y. Li, E. Wang, X. Xu, Y. Ma, Inorg. Chem. 5 (2006) 2055–2060. (a) V. Shivaiah, P.V. Reddy, L. Cronin, S.K. Das, J. Chem, Soc., Dalton Trans. (2002) 3781; (b) H.Y. An, D.R. Xiao, E.B. Wang, Y.G. Li, L. Xu, New J. Chem. 29 (2005) 854; (c) H. An, Y. Li, E. Wang, D. Xiao, C. Sun, L. Xu, Inorg. Chem. 17 (2005) 6062–6070; (d) H. An, Y. Li, D. Xiao, E. Wang, C. Sun, Cryst. Growth Des. 5 (2006) 1107–1112. C.D. Wu, C.Z. Lu, H.H. Zhuang, J.S. Huang, J. Am. Chem. Soc. 124 (2002) 3836. P.J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem. Int. Ed. 38 (1999) 3165. (a) J. Lu¨, E.H. Shen, Y.G. Li, D.R. Xiao, E.B. Wang, L. Xu, Cryst. Growth Des. 5 (2005) 65–67; (b) C.M. Liu, D.Q. Zhang, D.B. Zhu, Cryst. Growth Des. 5 (2005) 1639–1642; (c) Y. Lu, Y. Xu, E.B. Wang, J. Lu, C.W. Hu, L. Xu, Cryst. Growth Des. 5 (2005) 257–260; (d) M. Liu, D.Q. Zhang, M. Xiong, D.B. Zhu, Chem. Commun. (2002) 1416–1417. (a) M.I. Khan, E. Yohannes, D. Powell, Chem. Commun. (1999) 23– 24; (b) M.I. Khan, E. Yohannes, R. Doedens, J. Angew. Chem. Int. Ed. 38 (1999) 1292–1294; (c) X.B. Cui, J.Q. Xu, H. Meng, S.T. Zheng, G.Y. Yang, Inorg. Chem. 43 (2004) 8005–8009. (a) K. Kalcber, Electroanalysis 2 (1990) 419; (b) X.L. Wang, E.B. Wang, Y. Lan, C.W. Hu, Electroanalysis 14 (2002) 1116. (a) H.T. Evans Jr., E. Prince, J. Am. Chem. Soc. 105 (1983) 4838– 4839; (b) C. Gimenez-Saiz, J.R. Galan-Mascaros, S. Triki, E. Coronado, L. Ouahab, Inorg. Chem. 34 (1995) 524–526; (c) I. Loose, M. Bo¨sing, R. Klein, B. Krebs, R.P. Schulz, B. Scharbert, Inorg. Chim. Acta. 263 (1997) 99–108; (d) C.Y. Sun, S.X. Liu, L.H. Xie, C.L. Wang, B. Gao, C.D. Zhang, Z.M. Su, J. Solid State Chem. 179 (2006) 2093–2100. (a) I. Loose, E. Droste, M. Bo¨ssing, H. Pohlmann, M.H. Dickman, C. Rosu, M.T. Pope, B. Krebs, Inorg. Chem. 38 (1999) 2688; (b) B. Botar, T. Yamase, E. Ishikawa, Inorg. Chem. Commun. 3 (2000) 579; (c) M. Bosing, A. Noh, I. Loose, B. Krebs, J. Am. Chem. Soc. 120 (1998) 7252. In a typical synthesis procedure for 1, Na2WO4 Æ 2H2O (3.3 g) was added to an aqueous solution of CH3COONa/CH3COOH buffer (pH 4.5) (40 ml), heated to 80 °C and then Bi2(SO4)3 (0.48 g) and NH4Cl (0.76 g) were added successively. The resulting mixture was stirred for half an hour, cooled to room temperature, and then filtered. During a few days, the mainly precipitated colorless columnar crystals of 1 were filtered, washed with cooled water, and finally dried in air (yield about: 40% based on W). Anal. Calcd for H70N7BiW12O62: H, 1.96; N, 2.74; Bi, 5.84; W, 61.75 (%); Found: H, 1.98; N, 2.72; Bi, 5.88; W, 61.76 (%); Selected FTIR data (cm1): 3351(vs), 1632(s), 958(s), 899(m), 656(m), 588(w), 564(w), 481(m). ˚, Crystal data for 1: monoclinic, C2/c, a = 18.206(4) A ˚ , c = 18.792(4) A ˚ , a = 90°, b = 102.81(3)°, c = 90°, b = 19.047(4) A ˚ 3, Z = 2, R1 (wR2) = 0.0472 (0.1110), CSD: 417011. V = 6355(2) A D. Brown, D. Altermatt, Acta Crystallogr. B 41 (1985) 244–247.
A novel bismuth ion-bridged chainlike assembly from paradodecatungstate [H2W12O42]10 anions: (NH4)7[Bi(H2W12O42)] Æ 20H2O Zhen-He Xu, Xin-Long Wang, Yang-Guang Li, En-Bo Wang *, Chao Qin, Yan-Ling Si Key Laboratory of Polyoxometalate Science of Ministry of Education, Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun Jilin 130024, People’s Republic of China Received 30 September 2006; accepted 7 November 2006 Available online 16 November 2006
Abstract A new polyoxotungstate (NH4)7[Bi(H2W12O42)] Æ 20H2O has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, TG analysis and single-crystal X-ray diffraction. The most interesting structural feature of 1 is that the paradodecatungstate [H2W12O42]10 anions are linked, for the first time, by the trivalent main group atom BiIII which appeared commonly as a heteroatom in polyoxometalate chemistry, into a one-dimensional chainlike structure. Ó 2006 Elsevier B.V. All rights reserved. keywords: Polyoxometalates; Crystal structure; Bismuth; Tungstate
Polyoxometalates (POMs), as one kind of significant metal oxide cluster with nanosizes and abundant topologies, have been attracting extensive interest in fields such as catalysis, electrochemistry, electrochromism and magnetism [1]. The evolution of polyoxometalate chemistry is dependent upon the synthesis of new solids possessing unique structures and properties. Although synthesis of the materials remains a challenge, a large number of novel polyoxoanions with unexpected shapes and sizes are still being discovered [2]. Therefore, the self–assembly process of nanoscale polyoxometalates has attracted the attentions of many groups, and a series of the novel POMs possessing unique structure and properties have been reported [3]. It is noteworthy that one of the intriguing fields in the polyoxometalate chemistry is to find some novel subunits and then connect them into one-, two-, even three-dimensional (1D, 2D, even 3D) extended networks, either through direct condensation to form oxo-bridged arrays *
Corresponding author. Tel./fax: +86 431 5098787. E-mail addresses: [email protected], wangenb889@nenu. edu.cn (E.-B. Wang). 1387-7003/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2006.11.004
of clusters or through transition metal coordination complexes acting as inorganic bridging ligands [4]. To date, the commonly used polyoxometalate building blocks are still limited to well-known Keggin- [5], Wells–Dawson[6], Anderson- [7], Silverton- [8], and Lindquist-type [9] anions et al., and furthermore, the most extended frameworks based on these polyanions are achieved via the bridges of metal-organic complexes [10]. In contrast, bridging suitable metal oxide building blocks by simple linking units to generate true metal oxide surfaces and framework materials without the incorporation of additional conventional ligands still remains largely unexplored [11]. This kind of material is usually stable and insoluble in common organic solvent, whose property is very advantageous to expand application of POM–based materials in chemically bulk–modified electrode [12]. Among the various types of polyanions, the paradodecatungstate anion [H2W12O42]10 possesses some particular structural features, and provides a variety of possibilities of intermolecular linkages [13]. However, examples utilizing of this anion for the design and synthesis of POMs with extended structures are rarely reported. On
Z.-H. Xu et al. / Inorganic Chemistry Communications 10 (2007) 276–278
the other hand, as we know, the trivalent main group atom BiIII, similar to the PV and AsV atoms of the same main group, is exclusively act as heteroatom in the reported POM compounds [14]. Up to now no cases have been observed in which bismuth atom serve as a linker to assist the self-assembly of POM building blocks. Fortunately, here we reported a one-dimensional chainlike compound (NH4)7[Bi(H2W12O42)] Æ 20H2O 1 that is formed, for the first time, by linking [H2W12O42]10 clusters with Bi atoms. To our knowledge, 1 represents the first characterized POM compound containing Bi atoms as bridges. The title compound was synthesized from aqueous media and isolated as colorless columnar crystals [15]. Single-crystal X-ray diffraction analysis [16] shows that compound 1 exhibits a novel 1D structure built from paradodecatungstate [H2W12O42]10 units linked by Bi cation to yield a polymeric chain. The paratungstate–B units is structurally identical to those reported previously, e.g. K6[Co(H2O)4]2 Æ [H2W12O42] Æ 14H2O, Na2[H2W12O42] Æ 20H2O, Mg5[H2W12O42] Æ 38H2O [13]. As shown in Fig. 1, this polyoxoanion is centrosymmetric and consists of four corner–sharing groups of two types, each type containing three edge-sharing WO6 octahedra. All tungstate sites exhibit +VI oxidation state, possessing octahedral coordination geometry with different distortion extents. The +VI oxidation state is also confirmed by bond valence sum calculations [17], which gives the values of 6.204(44), 6.417(05), 5.894(79), 5.926(24), 6.003(04) and 5.975(81) for W(1), W(2), W(3), W(4), W(5) and W(6). The average value for the calculated oxidation states of W is 6.070(22), showing that all W sites are in the +6 oxidation state. This result is consistent with the formula of the title compound given by X-ray structure determination. The W–O bonds can be divided into four groups: (i) tung˚ ; (ii) tungsten–terminal oxygen, 1.708(15)–1.734(15) A sten–oxygen linked to bismuth atom, 2.348(13)–2.525(16) ˚ ; (iii) tungsten–bridging oxygen, 1.770(14)–2.229(16) A ˚; A (iv) tungsten–internal oxygen common to three tungsten ˚ . These results shows that atoms, 1.900(14)–2.2501(13) A WO6 octahedra of anions are severely distorted, indicating that the strong interaction between the polyanions and Bi cations. In compound 1, the [H2W12O42]10 cluster acts as tetradentate ligands coordinating to two Bi ions through terminal oxygen atoms of four WO6 belonging to the belt–
Fig. 1. Combined polyhedral/ball-and-stick representation of 1. The purple octahedra represent WO6 and the balls represent Bi (cyan) and O (red). (For interpretation of the references in colour in this figure legend, the reader is referred to the web version of this article.)
277
Fig. 2. Polyhedral representation of the 1D ‘‘zig-zag’’ chain in 1.
type W3O14 groups (Fig. 2). The coordination site of the bismuth ions might be described as a distorted pseudotrigonal bipyramid BiO4X with the lone pair X occupying an axial position, and the bismuth–oxygen distances are ˚ and the angles of in the range of 2.346(12)–2.518(15) A Bi–O–Bi are in the range of 78.9(4)–153.3(6)°. Compared with all known extended structures based on [H2W12O42]10 anion in which adjacent anions are connected by transition metal ions, compound 1 represents the first characterized paradodecatungstate containing the fifth main group element as bridges. In the IR spectrum of the title compound, the characteristic bands at 958, 899, 656, 588, 564, and 481 cm1are attributed to the W = O and W–O–W vibrations. Comparing the IR spectrum of compound 1 with that of [H2W12O42]10 [13], it can be observed that the shape of the peaks in the range 400–1000 cm1 is nearly identical to that of [H2W12O42]10 except slight shifts of some peaks due to the effect of coordination, which indicates that the polyanion in the title compound still retains the basic [H2W12O42]10 structure. This is in agreement with the result of single-crystal X-ray diffraction analysis. The IR spectrum studies indicate that there is strong interaction between the polyanions and bismuth ions in solid state. Thermogravimetric analysis of compound 1 shows four weight loss steps in the range of 40–770 °C (Fig. 3), corresponding to the release of all crystalline water molecules, and the NH3 molecules derived from the decomposition of NHþ 4 ions as well as the H2O water molecule forms derived from the combination of H and O atoms in the compound, respectively. The total weight loss of 14.13%
Fig. 3. The TG curve of compound 1.
278
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agrees with the calculated value of 14.18%. It can be observed that the result of the TG analysis agrees with that of the structure determination. In summary, we have reported a novel chain-like extended structure based on paradodecatungstate polyanion and Bi cation linker. The synthesis of compound 1 from well-defined discrete building blocks indicates that the diversity of pathways using metastable precursors to synthesize novel structures and species. Under similar conditions, some extended experiments can be done: it is possible to incorporate many other electrophiles, e.g. rare earths, and many possible novel species are very likely to be obtained. Now, we are exploring this avenue.
[6]
[7]
[8] [9]
Acknowledgement [10]
This work was supported by the National Science Foundation of China (No. 20371011). Appendix A. Supplementary materials Crystal data and structure refinement, atomic coordinates, bond lengths and angles, anisotropic displacement parameters, and IR spectra of compound 1 was available from the authors on request. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.inoche.2006.11.004.
[11]
[12]
References [13] [1] (a) M.T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin, 1983; (b) J.S. Anderson, Nature 140 (1937) 850; (c) C.L. Hill, Chem. Rev. 98 (1998) 1; (d) B.B. Xu, Z.H. Peng, Y.G. Wei, D.R. Powell, Chem. Commun. (2003) 2562; (e) L.C. Baker, D.C. Glick, Chem. Rev. 98 (1998) 3. [2] (a) R.C. Howell, F.G. Perez, S. Jain, W.D. Horrocks, J.A.L. Rheingold, L.C. Francesconi, Angew. Chem. Int. Ed. 40 (2001) 4031; (b) P. Mialane, A. Dolbecq, J. Marrot, E. Rivie`re, F. Se´cheresse, Chem. Eur. J. 11 (2005) 1771; (c) S. Reinoso, P. Vitoria, L.S. Felices, L. Lezama, J.M. Gutie´rrezZorrilla, Chem. Eur. J. 11 (2005) 1538; (d) S.T. Zheng, J. Zhang, G.Y. Yang, Inorg. Chem. 44 (2005) 2426; (e) J.Y. Niu, D.J. Guo, J.P. Wang, J.W. Zhao, Cryst. Growth Des. 4 (2004) 241. [3] (a) Y. Xia, P.F. Wu, Y.G. Wei, Y . Wang, H.Y. Guo, Cryst. Growth Des. 6 (2006) 253; (b) X.B. Cui, J.Q. Xu, H. Meng, S.T. Zheng, G.Y. Yang, Inorg. Chem. 43 (2004) 8005; (c) J.Y. Niu, Q. Wu, J.P. Wang, J. Chem. Soc., Dalton Trans. (2002) 2512. [4] B. Yan, Y. Xu, X. Bu, N.K. Goh, L.S. Chia, G.D. Stucky, J. Chem. Soc. Dalton Trans. (2001) 2009–2014. [5] (a) M. Sadakane, M.H. Dickman, M.T. Pope, Angew. Chem., Int. Ed. 39 (2000) 2914; (b) J.M. Galan-Mascaros, C. Gimenez-Saiz, S. Triki, C.J. GomezGarcia, E. Coronado, L. Ouahab, Angew. Chem., Int. Ed. Engl. 34 (1995) 1460;
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