Silver(i) coordination complexes and extended networks assembled from S, Se, Te substituted acenaphthenesDedicated to Professor David Cole-Hamilton on the occasion of his retirement and for his outstanding contribution to transition metal catalysis.Electronic supplementary information (ESI) available: X-ray crystal structure data; tables and figures. CCDC 889480-889485. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt31390a

Six related organo-chalconium silver( i ) coordination complexes, including two examples of rare organotellurium-silver coordination, have been prepared and structurally characterised by X-ray crystallography. The series of 5-bromo-6-(phenylchalcogeno)acenaphthene ligands L1-L3 [Acenap(Br)(EPh)] (Acenap = acenaphthene-5,6-diyl; E = S, Se, Te) were independently treated with silver( i ) salts (AgBF 4 , AgOTf). In order to keep the number of variables to a minimum, all reactions were carried out using a 1 : 1 ratio of Ag/L and run in dichloromethane. The nature of the donor atoms and the coordinating ability of the respective counter-anion affects the structural architecture of the final silver( i ) complex, generating a monomeric dinuclear complex {[(AgBF 4 ( L1 ) 2 ) 2 ] 1 }, monomeric, mononuclear, two-coordinate silver( i ) complexes {[AgBF 4 (L) 2 ] ( 2 L = L2 ; 3 L = L3 )}, a monomeric three-coordinate silver( i ) complex {[AgOTf( L2 ) 2 ] 5 }, a monomeric four-coordinate silver( i ) complex {[AgOTf( L1 ) 3 ] 4 } and a 1D extended helical chain polymer {[AgOTf( L3 )] n 6 }. The organic acenaphthene ligands L1-L3 all adopt the same ligation mode with the central silver atom (classical monodentate coordination), which employs a variety of coordination geometries (linear, trigonal planar, see-saw, tetrahedral). Chalcogen silver bonding leads to a range of coordination polymers depending on the nature of the chalcogen and the counterion.