The deliberate synthesis of the Keplerate [K(20) subset{(W)W(5)O(21)(SO(4))}(12)(VO)(30)(SO(4))(H(2)O)(63)](18-) with 20 pores all closed by K(+) in a supramolecular fashion proves that it is possible to follow new routes in polyoxotungstate chemistry based on pentagonal {(W)W(5)}-type units and to tune magnetic exchange couplings in {(M)M(5)}(12)M'(30) type Keplerates.
