Elusive Network Topology of a 5‑Connected Self-Catenated 3D Coordination Polymer: Featuring Ligand Formation via the In Situ S–S Bond

This article describes the synthesis of a new Zn(II)-based three-dimensional coordination polymer (3D CP) [Zn2(4,4′-dsb)2(4,4′-bpy)3]·(solvent)x [H24,4′-dsb = 4,4′-disulfanediyldibenzoic acid and 4,4′-bipyridine (4,4′-bpy)] (1). Here, the originally used 4-mercaptobenzoic acid (4-mba) undergoes in situ dimerization via the S–S bond to produce H24,4′-dsb. Fascinatingly, compound 1 exhibits a scarcely reported self-catenated 5-connected underlying net with point symbol {42·68}. As far as our knowledge is concerned, this tangled network is the first of this kind among CPs. The calculated highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) band gap computed from density functional theory (DFT) calculation along with well-corroborated experimental values obtained by Tauc’s plot reveals the conducting nature of the synthesized material