Synthesis, structures and properties of Ag+ complexes containing polyphosphine ligands with extended Ag⋯C, N-O⋯π and C-H⋯π interactions

• Three new silver (I) complexes have been synthesized and characterized.
• The change of polyphosphine ligands results in the formation of different types of polynuclear structures.
• Intermolecular weak interactions may be the key of construction of 1D infinite chains or 2D networks.

Based on ligands of N,N-bis((diphenylphosphino)methyl)benzenamine (pba), 4-(4-(bis((diphenylphosphino)methyl)amino)benzyl)-N-((diphenylphosphino)methyl)benzenamine (dptp) and N,N,N′,N′-tetrakis((diphenylphosphino)methyl)benzene-1,4-diamine (pbaa), three new silver(I) complexes [Ag(pba)2]ClO4 (1), [Ag2(dptp)2](ClO4)2·2DMF (2) and [Ag4(pbaa)(NO3)4]n (3), have been synthesized and characterized. Structural analysis reveals that all of these complexes contain the 1D infinite chains, with different variations in the weak interactions. Complexes 1 and 2 are interconnected by intermolecular C-H⋯π interactions to form 1D infinite chains and 2D networks, and the ordered-layer-lattic ClO4− and DMF in 2 are between 2D networks. For 3, the pbaa ligand adopts a tetradentate coordination mode to link two adjacent stair-like [Ag4O4] cores resulting in a 1D chain, respectively, with Ag⋯C, N-O⋯π and C-H⋯π interactions. All these show that phosphine ligands play an important role in the construction of interesting topological structures with different types of the weak interactions.

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