Self-organization of metallo-supramolecular polymer networks by free formation of pyridine–phenanthroline heteroleptic complexes

Abstract

Nature employs spontaneous self-organization of supramolecular bonds to create complex matter capable of adaptation and self-healing. Accordingly, the self-sorting of unlike ligands towards a cooperative heteroleptic complex or narcistic homoleptic...

Coordination Geometry and Mineralization in Self-Healing Mussel-Inspired Hydrogels

“…To further tweak the complexation geometry, we changed the Lig:M ratio. Of course, decreasing the metal ion concentration, or increasing the Lig:M ratio to 3, is expected to promote the fraction of the tris complexes, and similarly, mono complexes should prevail at Lig:M ≤1; however, the thermodynamic preference of the coordination geometry is of high significance and can completely outweigh the effect of the Lig:M ratio. , In accordance with the effect of OH content, promoting the formation of tris complexes results in lowering the plateau modulus and relaxation time along with the convergence of the terminal moduli slopes to the characteristics of a single Maxwell mode, as shown in Figure c. Oppositely, the increase of mono complexes at high metal ion concentrations results in the decrease of the network connectivity and stability, however, with broadening of the main relaxation process, and pronounced emergence of a low-frequency relaxation mode.…”

The network structure in transient telechelic polymer networks: extension of the Miller–Macosko model

“…7,21,48,49 Moreover, the coordination geometry of monodentate ligands like pyridine and imidazole has been reported to significantly depend on the utilized metal ion. 8,50 We have gathered some examples of the thermodynamic equilibrium constants of various tri-, bi-, and monodentate ligands in forming complexes with various geometries with specific metal ions, as reported in Tables S1–S3 (ESI†). This information gives us a sensible range of equilibrium constants to be considered in our parametric study.…”