Synthesis and Structural Characterization of a Series of Capped Keggin Derivates

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摘要 Hydrothermal reactions of Na₂MoO₂·2H₂O and NH₄VO₃ (or V₂O₅) with appro- priate reducing agents such as organic amines, NH₂OH·HCl and Mo(CO)₆ gave rise to the forma- tion of a series of capped Keggin derivatives, [N(CH₃)₄]₂Na₃(NH₄)₂[(V^VO₄)Mo^VI₈V^IV₄O₃₆(V^IVO)₂]·13H₂O (1), [NH₄]₇[(V^VO₄)Mo^VI₈V^IV₄O₃₆(V^IVO)₂]·7H₂O (2), [HN(CH₂CH₂)₃NH][(PO₄)Mo^V₃Mo^VI₉O₃₆(V^IVO)₂]·3[N(CH₂CH₂)₃N]·(en)·4.5H₂O (3) and [HNH₂OH][NH₄]₂[(V^VO₄)Mo^VI₈V^IV₄O₃₆(V^IVO)₄]·24H₂O (4). Single-crystal X-ray diffraction analysis revealed that the anions in 1～3 are two-capped Keggin derivatives with characteristic trans vanadium-oxygen caps, whereas the heteropoly anion in 4 is a tetra-capped α-Keggin derivative with characteristic vanadium-oxygen caps on the equatorial plane.

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	姜琦斐
	杨文斌
	吴小园
	卢灿忠

关键词 ： heteropoly polyoxometalates, capped Keggin derivatives, hydrothermal synthesis and crystal structures , DOI: 10.14102/j.cnki.0254-5861.2011-0353

Abstract：Hydrothermal reactions of Na₂MoO₂·2H₂O and NH₄VO₃ (or V₂O₅) with appropriate reducing agents such as organic amines, NH₂OH·HCl and Mo(CO)₆, gave rise to the formation of a series of capped Keggin derivates, [N(CH₃)₄]₂Na₃(NH₄)₂[(V^VO₄)Mo^VI₈V^IV₄O₃₆(V^IVO)₂]·13H₂O (1), [NH₄]₇[(V^VO₄)Mo^VI₈V^IV₄O₃₆(V^IVO)₂]·7H₂O (2), [HN(CH₂CH₂)₃NH][(PO₄)Mo^V₃Mo^VI₉O₃₆(V^IVO)₂]·3[N(CH₂CH₂)₃N]·(en)·4.5H₂O (3) and [HNH₂OH][NH₄]₂[(V^VO₄)Mo^VI₈V^IV₄O₃₆(V^IVO)₄]·24H₂O (4). Single-crystal X-ray diffraction analysis revealed that the anions in 1～3 are two-capped Keggin derivatives with characteristic trans vanadium-oxygen caps, whereas the heteropoly anion in 4 is a tetra-capped α-Keggin derivative with characteristic vanadium-oxygen caps on the equatorial plane.

Key words： heteropoly polyoxometalates capped Keggin derivatives hydrothermal synthesis and crystal structures DOI: 10.14102/j.cnki.0254-5861.2011-0353

收稿日期: 2014-04-25 出版日期: 2014-07-15

基金资助:Supported by the 973 key program of the MOST (2010CB933501, 2012CB821705), the Chinese Academy of Sciences (KJCX2-YW-319, KJCX2-EW-H01), the National Natural Science Foundation of China (21373221, 21221001, 91022008, 91122027, 51172232) and the Natural Science Foundation of Fujian Province (2011HZ0001-1, 2012J06006, 2006L2005)

通讯作者: 卢灿忠 E-mail: czlu@fjirsm.ac.cn

引用本文:

姜琦斐;杨文斌;吴小园;卢灿忠. Synthesis and Structural Characterization of a Series of Capped Keggin Derivates[J]. 结构化学, 2014, 33(11): 1703-1712.
JIANG Qi-Fei;YANG Wen-Bin;WU Xiao-Yuan;LU Can-Zhong. Synthesis and Structural Characterization of a Series of Capped Keggin Derivates. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2014, 33(11): 1703-1712.

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http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2014/V33/I11/1703

(1) Pope, M. T.; Müller, A. Polyoxometalate chemistry – an old field with new dimensions in several disciplines. Angew. Chem. Int. Ed. Engl. 1991, 30, 34–48.

(2) A comprehensive review on polyoxometalates has been given by Prof. Hill, et. al. Chem. Rev. 1998, 98, 1–389.

(3) Dolbecq, A.; Dumas, E.; Mayer, C. R.; Mialane, P. Hybrid organic-inorganic polyoxometalate compounds: from structural diversity to applications Chem. Rev. 2010, 110, 6009–6048.

(4) Wang, X.; Liu, L.; Zhang G.; Jacobson, A. J. An extended chain structure formed by covalently linking polyoxovanadate cages with tetrahedral six rings. Chem. Commun. 2001, 2472–2473.

(5) Muller, A.; Krickemeyer, E.; Bogge, H.; Schmidtmann, M.; Peters, F.; Menke, C.; Meyer, J.An unusual polyoxomolybdate: giant wheels linked to chains. Angew. Chem. Int. Ed. Engl. 1997, 36, 484–486.

(6) Hagrman, P. J.; Hagrman, D.; Zubieta, J. Organic-inorganic hybrid materials: from "simple" coordination polymers to organodiamine-templated molybdenum oxide. Angew. Chem. Int. Ed. Engl. 1999, 38, 2639–2684.

(7) Binnemans, K. Lanthanide-based luminescent hybrid materials. Chem. Rev. 2009, 109, 4283–4373.

(8) Nohra, B.; Moll, H. E.; Albelo, L. M. R.; Mialane, P.; Marrot, J.; Mellot- Draznieks, C.; O’Keeffe, M.; Biboum, R. N.; Lemaire, J.; Keita, B.; Nadjo, L.; Dolbecq, A. Polyoxometalate-based metal organic frameworks (POMOFs): structural trends, energetics, and high electrocatalytic efficiency for hydrogen evolution reaction. J. Am. Chem. Soc. 2011, 133, 13364–13374.

(9) Yang, W.; Lu, C.; Lin, X.; Zhuang H.; Huang, J. (NH₄)₁₅[H₃Mo₅₇V₆(NO)₆O₁₈₉(H₂O)₁₂(VO)₆]·60H₂O: new nanocompound obtained by chemical embellishment of {M₅₇V₆}. Inorg. Chem. 2000, 39, 2706–2707.

(10) Yang, W.; Lu, C.; Lin, X.; Zhuang, H. A novel acetated 54-member crown-shaped polyoxomolybdate with unprecedented structural features: Na₂₆[{Na(H₂O)₂}₆({μ₃-OH)₄Mo^V₂₀Mo^VI₃₄O₁₆₄(μ₂-CH₃COO)₄}]·120H₂O. Chem Commun. 2000 1623-1624; (b) Yang, W.; Lu, C.; Lin, X.; Zhuang, H. Novel acetate polyoxomolybdate “host” accommodating a zigzag-chainlike “guest” of five edge-shared sodium cations: Na₂₁{[Na₅(H₂O)₁₄][Mo₄₆O₁₃₄(OH)₁₀(CH₃COO)₄]}·CH₃COONa·≈95H₂O. Inorg. Chem. 2002, 41, 452–454.

(11) Yang, W.; Lu, C.; Zhan X.; Zhuang, H. Hydrothermal synthesis of the first vanadomolybdenum polyoxocation with a “metal-bonded” spherical framework. Inorg. Chem. 2002, 41, 4621−4623.

(12) Sheldrick, G. M. SADABS, Siemens Analytical X-ray Instrument Division. Madison, WI 1995.

(13) Sheldrick, G. M. Universität Görringen, Germany 1997.

(14) Soghomonian, V.; Chen, Q.; Haushalter, R. C.; Zubieta, J. Vanadium phosophate framework solid constructed of octahedral, square pyramids, and tetrahedra with a cavity dimension of 18.4 Å. Angew. Chem. Int. Ed. Engl. 1993, 32, 610–612.

(15) Khan, M. I.; Meyer, L. M.; Haushalter, R. C.; Schweitzer, A. L.; Zubieta, J. Dye, J. L. Giant voids in the hydrothermally synthesized microporous square pyramidal tetrahedral framework vanadium phosphates [HN(CH₂CH₂)₃NH]K[V₅O₉(PO₄)₂]·xH₂O and Cs₃[V₅O₉(PO₄)₂]·xH₂O. Chem. Mater. 1996, 8, 43–53.

(16) Zhang, Y.; Haushalter, R. C.; Clearfield, A. A heteropolyanion containing two linked mixed Mo/V pentadecaoxometalate clusters: structure of [Mo₁₆V₁₄O₈₄]^14-. J. Chem. Soc. Chem. Commun. 1995, 1149–1150.

(17) Müller, A.; Koop, M.; Schiffels, P.; Bogge, H. [{Mo^VI₈V^IV₄O₃₆(V^VO₄) (V^IVO)₂}_n]^7n-: capped α-Keggin fragments linked to a chain. Chem. Commun. 1997, 1715–1716.

(18) Brese, N. E.; O’Keeffe, M. Bond-valence parameters for solids. Acta. Crystallogr. 1991, B47, 192–197.

(19) Xu, Y.; Zhu, H.; Cai, H.; You, X. [Mo^V₂Mo^VI₆V^IV₈O₄₀(PO₄)]^5–: the first polyanion with a tetra-capped Keggin structure.Chem. Commun. 1999, 787–788.

(20) Xu, Y.; Zhu, D.; Guo, Z.; Shi, Y.; Zhang, K.; You, X. Cation-induced assembly of the first mixed molybdenum-vanadium hexadecametal host shell cluster anions. J. Chem. Soc., Dalton. Trans. 2001, 772–773.