Molybdophosphonate clusters as building blocks in the oxomolybdate-organodiphosphonate/cobalt(II)-organoimine system: structural influences of secondary metal coordination preferences and diphosphonate tether lengths

Inorganic Chemistry
N Gabriel ArmatasJon Zubieta

Abstract

Hydrothermal conditions have been used in the preparation of a series of organic-inorganic hybrid materials of the cobalt-molybdophosphonate family. The reactions of MoO(3), cobalt(II) acetate or cobalt(II) acetylacetonate, tetra-2-pyridylpyrazine (tpyprz), and organodiphosphonic acids H(2)O(3)P(CH(2))nPO(3)H(2) (n = 1-5 and 9) of varying tether lengths yielded compounds of the general type {Co(2)(tpyprz)(H(2)O)(m)}4+/MoxOy{O(3)P(CH(2))(n)PO(3)}z. The recurring theme of the structural chemistry is the incorporation of {Mo(5)O(15)(O(3)PR)(2)}(4-) clusters as molecular building blocks observed in the structures of nine phases (compounds 2-9 and 11). The structural consequences of variations in reaction conditions are most apparent in the series with propylene diphosphonate, where four unique structures 4-7 are observed, including two distinct three-dimensional architectures for compounds 5 and 6 whose formulations differ only in the number of water molecules of crystallization. With pentyldiphosphonate, a second phase 10 is obtained which exhibits a unique cluster building block, the hexamolybdate [Mo(6)O(18){O(3)P(CH(2))(5)PO(3)}](4-). In the case of methylenediphosphonic acid, a third structural motif, the trinuclear {(Mo(3)O(8...Continue Reading

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Citations

Jan 1, 2010·Acta Crystallographica. Section E, Structure Reports Online·Paul Deburgomaster, Jon Zubieta
Sep 10, 2014·Inorganic Chemistry·Joanna Palion-GazdaMiguel Julve
Dec 23, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Hong-Xin MaLan-Cui Zhang
Sep 24, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaopeng SunJingyang Niu
Apr 24, 2012·Chemistry : a European Journal·Jingyang NiuJingping Wang
May 11, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Susan Kunnas-HiltunenMarkku Ahlgrén
Oct 16, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Jian-Ping WangZai-Ming Zhu
Feb 16, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Fengyan Li, Lin Xu
Nov 21, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Weisong ZhangZhenhui Kang
Nov 11, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·D Elias Jesu Packiam, Kanamaluru Vidyasagar

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