Assembly of organosilver coordination frameworks with aromatic ligands bearing a terminal enediyne group

In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H2L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H2L2), each resulting ethynide ligand is invariably inserted into a Agn (n = 3–4) basket, leading to the generation of coordination chains or multinuclear metallocycles, but the well shielded ethenyl group does not take part in silver–olefin binding. In (Ag2L1)·9AgCF3CO2·3H2O·3CH3CN and (Ag2L1)2·9AgCF3CO2·11H2O, which can be crystallized in different polar protic solvent media, an infinite chain composed of metallocycles is favorably generated with the assistance of silver–aromatic interaction; such chains are further interconnected to form a two- or three-dimensional organosilver network. In (Ag2L2)·5AgCF3CO2·5DMSO, the fluorenyl group does not participate in silver–aromatic interaction; however, its planar skeleton directs the construction of a more closely packed metal–organic coordination chain.

Graphical abstractA series of five silver(I) complexes synthesized with aromatic ligands each bearing a terminal enediyne group has been characterized by single crystal X-ray analysis. The coordination preferences between the resulting ethynide ligands with ancillary trifluoroacetate proved to be dominant factors in directing the construction of organosilver networks composed of chains or metallocycles, which are further consolidated by argentophilic, silver–aromatic, and weak intermolecular hydrogen-bonding interactions in supramolecular assembly.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlight►First structural study of silver(I) trifluoroacetate complexes containing aromatic ligands each bearing a terminal enediyne group. ►Network assembly with multinuclear silver-ethynide supramolecular synthon. ►Organosilver networks consolidated by argentophilic, silver-aromatic, and weak intermolecular hydrogen-bonding interactions.