The synthesis of a new triaminoguanidinium‐based ligand with three tris‐chelating [NNO]‐binding pockets and C3 symmetry is described. The reaction of tris‐(2‐pyridinylene‐N‐oxide)triaminoguanidinium salts with zinc(II) formate leads to the formation of cyclic supramolecular coordination compounds which in solution bind fullerenes in their spherical cavities. The rapid encapsulation of C60 can be observed by NMR spectroscopy and single‐crystal X‐ray diffraction and is verified using computation.

The reaction of C3‐symmetric tris‐(2‐pyridinylene‐N‐oxide)triaminoguanidinium salts ([H3L]X) and zinc(II) in presence of thiocyanate and different carboxylate ions as co‐ligands yields in a series of different coordination compounds. Supramolecular metallocycles and carboxylate‐bridged dimers are defined by two fundamentally different binding motifs. By adjusting the co‐ligands’ stoichiometry, metallocycles and carboxylate‐bridged compounds can be synthesized selectively. Furthermore, the occupation of the metallocycles with co‐ligands can also be controlled that way. Directed synthesis of these metallocycles is essential for further application in host‐guest chemistry due to their cavities and porosity in the solid state.

Phosphinate and phosphane substituted hierarchical helicates have been prepared, and the phosphinate derivatives could be characterized in the crystal. The helicate with phosphane substituents was submitted to an orientating study on catalysis, showing its potential to act as chelating ligand for the generation of active rhodium‐based hydrogenation catalysts.

Novel cobalt(II) containing compounds of tris‐(2‐pyridinylene‐N‐oxide)triaminoguanidine ligands L2− are presented: the supramolecular metallocycle [Co6(OOCMe)3(NCS)3L3]4 and the one‐dimensional coordination polymer {[Co3(μ‐OOCMe)3L]NO3}n. Analog zinc(II) complexes show similar to identical structures that are slightly influenced by different preferences regarding the coordination number. In the polymers, the coordination number is five, which is less common for zinc(II) and rare for cobalt(II). The compounds are characterized by single‐crystal as well as powder X‐ray diffraction, IR spectroscopy, and ESI mass spectrometry. Magnetic measurements revealed predominantly antiferromagnetic exchange interaction between the cobalt(II) centers linked by the triaminoguanidine backbone.