Stepwise Synthesis of Charged and Neutral Two-Dimensional Networks via One-Dimensional Silver(I) Coordination Polymer Based on Bis(4-pyridylmethyl)sulfide

Stepwise synthesis and structural characterization of two-dimensional (2-D) coordination polymer frameworks with positive charged or neutral cavities are reported. First, reactions of bis(4-pyridylmethyl)sulfide (L) with silver salts (1: nitrate and 2: perchlorate) afforded the respective double-stranded one-dimensional (1-D) chains [Ag(L)NO3]n (1) and {[Ag2(L)2](ClO4)2}n (2), both of which are stabilized by face-to-face π−π interactions. In this case, the silver(I) center in the nitrato complex 1 shows four-coordinated distorted tetrahedral geometry, whereas that of the perchlorato complex 2 exhibits a distorted trigonal planar geometry. The difference of these structures indicates that the coordination ability of the anions has important effects on the silver(I) coordination environments. Interestingly, the perchlorato 1-D complex 2 allows further reactions with bridging ligands such as 4,4′-bipyridine (bpy) and terephthalate (tp2−) to give a 2-D positive-charged network {[Ag2(L)2(bpy)]·(ClO4)2·C6H6}n (3) and a 2-D neutral network {[Ag2(L)2(tp)]·2DMSO·6H2O}n (4), respectively. The nitrato 1-D complex 1, however, showed no reactivity with the bridging ligands in the same condition. The results show that the replacement of anion by the bridging ligand in the coordination sphere of the 1-D precursor plays crucial roles in determining the reactivity for the synthesis of higher dimensional open frameworks.