Syntheses, structures and luminescent properties of silver(I) coordination polymers based on aminopyrimidyl derivatives and 1,2,3,4-butanetetracarboxylic acid

Two mixed-ligand silver(I) coordination polymers (CPs) of the formula {[Ag4(mapym)2(butca)(H2O)4]·2H2O}n (1) and [Ag4(dmapym)6(butca)·2H2O]n (2) (mapym = 2-amino-4-methylpyrimidine, dmapym = 2-amino-4,6-dimethylpyrimidine, H4butca = 1,2,3,4-butanetetracarboxylic acid) were prepared by reactions of Ag2O and 2-aminopyrimidyl ligands with H4butca under the ammoniacal condition. Both complexes were characterized by element analysis, IR and X-ray single-crystal diffraction. In 1, a pair of μ2-mapym ligands bind four Ag(I) ions to form [Ag4(mapym)2] subunits which stack into one-dimensional (1D) chains via inter-subunit π⋯π interaction. The μ6-κ1:κ2:κ1:κ2-butca ligands extend the 1D chains into a two-dimensional (2D) sheet which can be simplified into a 44-sql net. When mapym was replaced by dmapym, we obtained 2 as a 1D chain incorporating μ6-κ1:κ2:κ1:κ2-butca and μ1-dmapym ligands. The dimensions of 1–2 decrease from 2D to 1D mainly due to the steric effect of methyl groups. Additionally, the hydrogen-bonding, π⋯π and C–H⋯π interactions also direct the self-assembly of supramolecular architectures. The photoluminescence properties of the 1 and 2 were investigated in the solid state at room temperature.