A Silver Bite: Crystalline Heterometallic Architectures Based on Ag–π Interactions with a Bis‐Dipyrrin Zinc Helicate

Abstract

An unprecedented mode of assembly of helical motives and Ag(I) ions in the crystalline state is described. The combination of a Zn(II) helicate based on a 2,2'-bisdpm bearing peripheral benzonitrile moieties with AgX salts, leads to the formation of a tetranuclear core containing Ag-π interactions. Depending on the coordinating ability of the X(-) anion and the solvents used, the tetranuclear complex self-assembles into coordination polymers of varying dimensionality. From the sequence of coordination events (Ag-π or Ag-peripheral site), one may envisage two possible construction scenarios. However, the Ag-π as primary event seems reasonable owing to the rather weak binding propensity of the nitrile group and the chelating nature of the π-clefts.