Anionic Hosts for the Incorporation of Cationic Guests

Pentaphosphaferrocene [Cp*Fe(η(5)‐P(5))] (1 a) represents an excellent building block for the template‐directed synthesis of spherical supramolecules. Here, the self‐assembly of 1 a with Cu(I) and Cu(II) halides in the presence of the template complexes [FeCp(2)][PF(6)], [CoCp(2)][PF(6)] and [CoCp(2)] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp(2)](+) is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp(2)]@[{1 a}(12)(CuBr)(17.3)] (3), [CoCp(2)](+) (3){[CoCp(2)](+)@[{1 a}(8)Cu(24.25)Br(28.25)(CH(3)CN)(6)](4−)} (4), {[Cp(2)Co](+)@[{1 a}(8)(CuI)(28) (CH(3)CN)(9.8)]}{[Cp(2)Co](+)@[{1 a)}(8)Cu(24.4)I(26.4)(CH(3)CN)(8)](2−)} (5), and [{1 a}(3){(1 a)(2)NH}(3)Cu(16)I(10)(CH(3)CN)(7)] (6), respectively.