Abstract
Six silver(I) coordination complexes have been prepared and structurally characterised. Mixed chalcogen-donor acenaphthene ligands L1–L3 [Acenap(EPh)(E'Ph)] (Acenap = acenaphthene-5,6-diyl; E/E' = S, Se, Te) were independently treated with silver(I) salts (AgBF4/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, the coordinating ability of the respective counter-anion and the type of solvent used in recrystallisation, all affect the structural architecture of the final silver(I) complex, generating monomeric, silver(I) complexes {[AgBF4(L)2] (1 L = L1; 2 L = L2; 3 L = L3), [AgOTf(L)3] (4 L = L1; 5 L = L3), [AgBF4(L)3] (2a L = L1; 3a L = L3)} and a 1D polymeric chain {[AgOTf(L3)]n 6}. The organic acenaphthene ligands L1-L3 adopt a number of ligation modes (bis-monodentate μ2-η2-bridging, quasi-chelating combining monodentate and η6-E(phenyl)-Ag(I) and classical monodentate coordination) with the central silver atom at the centre of a tetrahedral or trigonal planar coordination geometry in each case. The importance of weak interactions in the formation of metal-organic structures is also highlighted by the number of short non-covalent contacts present within each complex.
Highlights
Coordination chemistry is an integral feature of inorganic and bioinorganic chemistry [1,2,3,4], with many applications in polymer design and materials science [4,5,6,7]
The organic acenaphthene ligands L1-L3 adopt a number of ligation modes (bis-monodentate μ2-η2-bridging, quasi-chelating combining monodentate and η6-E(phenyl)-Ag(I) and classical monodentate coordination) with the central silver atom at the centre of a tetrahedral or trigonal planar coordination geometry in each case
Following the pioneering work on transition metal chemistry by Nobel Prize winning Swiss chemist Alfred Werner, the metal-ligand interaction emerged as an important tool for the manufacture of supramolecular metal complexes and is prominent in the design of organic solids and metal-organic frameworks (MOFs) [4,5,6,7,8,9,10,11,12,13,14]
Summary
Coordination chemistry is an integral feature of inorganic and bioinorganic chemistry [1,2,3,4], with many applications in polymer design and materials science [4,5,6,7]. Self-assembly, which dictates the structural motif of the final complex is controlled by experimental conditions [10,11,12,13,14] Factors such as the central metal ion oxidation state, the coordination geometry, the metal-to-ligand ratio, the nature and spacer length of the bridging ligand, the presence of solvents and the type of counter-anions, all play a significant role [10,11,12,13,14]. {[Acenap(EPh)] (E = S, Se)} [49,50,51] proved ideal building blocks for the assembly of supramolecular networks and extended structures, acting as bridging organic donor ligands between diversely coordinating silver(I) centres [54].
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