A small cavity with reactive internal shell atoms spanned by four {As(W/V)9}-type building blocks allows host-guest chemistry under confined conditions |
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Authors: | Müller Achim Pope Michael T Merca Alice Bögge Hartmut Schmidtmann Marc van Slageren Joris Dressel Martin Kurth Dirk G |
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Affiliation: | Lehrstuhl für Anorganische Chemie I, Fakult?t für Chemie der Universit?t, Postfach 100131, 33501 Bielefeld, Germany. a.mueller@uni-bielefeld.de |
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Abstract: | The reaction of [H2As(III)W18O60]7- with VO2+ and SO4(2-) ions in aqueous solution leads to a V(IV)/V(V) mixed-valence cluster anion containing the {As4M40O140}-type cryptand which has a high formation tendency. An important result is that it exhibits a new type of reactive internal cavity shell. The correspondingly obtained compound Na(NH4)20[{(V(IV)O(H2O))(V(IV)O)2(SO4)2}{(As(III)W9O33)2(As(III)W7.5V(V)1.5O31)2(WO2)4}] x 40 H2O (1), which can also be synthesized from a precursor with the preorganized cryptand, was characterized by elemental and thermogravimetric analyses (determination of crystal water content), redox titrations (determination of the number of V(IV) centers), electronic absorption as well as vibrational spectra, single-crystal X-ray structure analysis (including bond valence sum calculations), and magnetic susceptibility measurements. The relatively small central cavity--formed by the linking of four {AsM9}-type lacunary units (M = W/V) by four WO6 octahedra--allows positioning of a variety of cationic as well as anionic "guests" under confined conditions according to a new approach: replacement of some of the W by V atoms leads to high reactivity of the internal cavity shell as a result of relatively weak VO bonds compared to the WO bonds. This allows an interesting "encapsulation chemistry" with new options. In the present case the cavity contains besides an arrangement of three V(IV) centers, two sulfate groups that replace O atoms of the {AsM9} units as well as an interesting hydrogen bond situation. |
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Keywords: | cryptand encapsulation chemistry magnetism polyoxometalates tungsten vanadium |
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