Across the Dimensions: A Three-Component Self-Assembly of Pentaphosphaferrocene-based Coordination Polymers.

Pentaphosphaferrocenes [CpR Fe(η5 -P5 )] (Cp*=η5 -C5 Me5 ) (A), Cp''=η5 -C5 H3 tBu2 -1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF6 . Adding rigid aromatic dinitriles ortho/meta/para-(NC)2 C6 H4 in a one-pot reaction between [CpR Fe(η5 -P5 )] and AgSbF6 leads to various coordination polymers (CPs) by a three-component self-assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC)2 C6 H4 play a key role in the formation of the isolated CPs. All CPs were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction.

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 )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 Ag11 ]11+ (x=7) or (A)@[(A)12 Ag12 ]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 Ag12 ]12+ were visualized by transmission electron microscopy.