Self-Assembly of Organocyanide Dianions and Metal–Organic Macrocycles into Polymeric Architectures Including an Unprecedented Quadruple Helical Aperiodic Structure

A facile building block approach was employed for the self-assembly of metal–organic macrocyclic complexes and organocyanide dianions into one-dimensional coordination polymers. The conformation of the organocyanide dianions as well as π–π stacking and hydrogen bonding interactions were found to be critical factors that determine the formation of a particular structure. In the case of 1,3-dicyanamidobenzene dianion (DCNB 2– ) bridging ligands, the absence of water resulted in an unprecedented aperiodic quadruple helical structure in which the π–π stacking interaction dominates, whereas, in the presence of water, a zigzag chain compound in which hydrogen bonding interactions prevail is formed.