One-pot self-assembly reactions of the polyphosphorus complex [Cp*Fe(eta(5)-P-5)] (A), a coinage metal salt AgSbF6, and flexible aliphatic dinitriles NC(CH2)(x)CN (x=1-10) yield 1D, 2D, and 3D coordination polymers. The seven-membered backbone of the dinitrile was experimentally found as the borderline for the self-assembly system furnishing products of different kinds. At x<7, various rather simple polymers are exclusively formed possessing either 0D or 1D Ag/A structural motifs connected by dinitrile spacers, while at x >= 7, the self-assembly switches to unprecedented extraordinary 3D networks of nano-sized host-guest assemblies (SbF6)@[(A)(9)Ag-11](11+) (x=7) or (A)@[(A)(12)Ag-12](12+) (x=8-10) linked by dinitriles. The polycationic nodes represent the first superspheres based on A and silver and are host-guest able. All products are characterized by NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. The assemblies [(A)(12)Ag-12](12+) were visualized by transmission electron microscopy.