Supramolecular topology design of silver(i) and copper(ii) coordination polymers through a new semi-rigid sulfonyl ligand with different anion templates

Abstract

A series of metal organic coordination polymers (MOCPs) of silver(I) and copper(II) coordinated with a novel multifunctional semi-rigid sulfonyl ligand with different anion templates and oxidation states were designed for the first time. In addition, their atomically precise molecular structure was determined by single crystal X-ray diffraction analysis. In comparison, the topology of silver(I)-based MOCPs is affected significantly by different anion templates. The coordination modes are quite different with the anions varying: linear for ClO₄⁻, trilateral for CO₂CF₃⁻, and tetrahedral for CO₂C₂F₅⁻. Due to the difference of electron configurations between Ag(I) and Cu(II), the coordinated configuration of the metal center is also different. While the coordinated configuration of Cu(II) center tends to be placed in an octahedron. Furthermore, for the copper(II) MOCPs, the oxidation state of the L ligand also plays an important role. When the N atoms in L were oxidized, the coordination mode of Cu(II) became tetrahedral with Cu(II) stuck on the bottom of the conventional octahedral mode. In general, it is an effective and controllable strategy to mediate the coordination mode and aggregation of supramolecular assembly-based MOCPs through the combination of a multifunctional organic ligand and its corresponding oxidation state design; elaborate metallic species and electron configuration selection; and suitable anion template introduction to generate multiform and hierarchical non-covalent bond interactions including π–π interactions and hydrogen bond formation that afford their coordination mode diversity.