Three Dicyanidometallate(I)‐based Complexes Incorporating Hydrogen‐bonding, π–π Packing and d 10 –d 10 Interactions with Auxiliary 2,2′‐Bipyridyl‐like Ligands

To investigate the influence of the non‐covalent interactions, such as hydrogen‐bonding, π–π packing and d 10 –d 10 interactions in the supramolecular motifs, three cyanido‐bridged heterobimetallic discrete complexes {Mn(bipy) 2 (H 2 O)[Ag(CN) 2 ]}[Ag(CN) 2 ] ( 1 ), {Mn(phen) 2 (H 2 O)[Au(CN) 2 ]} 2 [Au(CN) 2 ] 2 · 4H 2 O ( 2 ), and {Cd(bipy) 2 (H 2 O)[Au(CN) 2 ]}[Au(CN) 2 ] ( 3 ) (bipy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline), which are based on dicyanidometallate(I) groups with 1:2 stoichiometry of metal ions and 2,2′‐bipyridyl‐like co‐ligands were synthesized and structurally characterized. In compound 1 , hydrogen bonding and π–π interactions governed the supramolecular contacts. In compound 2 , the incorporation of aurophilic, hydrogen bonding and π–π interactions result in a 3D supramolecular network. In compound 3 , hydrogen bonding and π–π stacking interactions result in a 2D supramolecular layer. In the three complexes, hydrogen‐bonding, π–π packing and/or d 10 –d 10 interactions can play important roles in increasing the dimensionality of supramolecular assemblies.