Three‐component Self‐Assembly Changes its Course: A Leap from Simple Polymers to 3D Networks of Spherical Host‐Guest Assemblies

One-pot self-assembly reactions of the polyphosphorus complex [Cp*Fe(η5-P5)] (A), a coinage metal salt AgSbF6 and flexible aliphatic dinitriles NC(CH2)xCN (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)9Ag11]11+ (x = 7) or (A)@[(A)12Ag12]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, MS spectrometry and single-crystal X-ray diffraction. The assemblies [(A)12Ag12]12+ were visualized by transmission electron microscopy.