Hydrothermal Synthesis and Structural Characterization of Three One-Dimensional Heteropolytungstates Formed by Mono-Copper(II)-Substituted Dawson or Keggin Cluster Units

摘要

Reactions of monovacant Dawson-/Keggin-polyoxoanions, formed in situ from trivacant Dawson-/Keggin-precursors, with copper complexes under hydrothermal conditions lead to three inorganic-organic hybrid polyoxotungstates [Cu(en)(2)(H2O)](2) {[Cu(en)(2)(H2O)](2)[Cu(en)(2)](4)[Cu(en)(2)][alpha(2)-P2W17CuO61](2)}ce nter dot(OH)(2)center dot 12H(2)O (1), [Cu(dap)(2)] [Cu(dap)(2)(H2O)](2)[alpha-PW11CuO39]center dot(OH)center dot 2H(2)O (2) and (H(2)en)(2)[alpha-PW11CuO39][Cu(en)(2) (H2O)(2)](0.5)center dot 1.5H(2)O (3) (en = ethylenediamine and dap = 1,2-diaminopropane). X-ray structural analyses demonstrate that 1 exhibits the first zigzag 1-D chain arrangement constructed from mono-copper(II)-substituted Dawson dimeric polyoxoanions [alpha(2)- P2W17CuO61](2)(16-) linked by [Cu(en)(2)](2+) bridges, whereas 2 and 3 display 1-D linear chain architectures made up of mono-copper(II)-substituted Keggin polyoxoanions [alpha-PCuW11O39](5-) linked together via corner-sharing MO6 octahedra (M = Cu or W).