Self-healing, luminescent metallogelation driven by synergistic metallophilic and fluorine–fluorine interactions

Square planar platinum(II) complexes are attractive building blocks for multifunctional soft materials due to their unique optoelectronic properties. However, for soft materials derived from synthetically simple discrete metal complexes, achieving a combination of optical properties, thermoresponsive, and excellent mechanical properties is a major challenge. Here, we report the rapid self-recovery of luminescent metallogels derived from platinum(II) complexes of perfluoroalkyl and alkyl derivatives of terpyridine ligands. Using single crystal X-ray diffraction studies we show that the presence of a synergistic platinum-platinum (Pt∙∙∙Pt) metallopolymerization and fluorine-fluorine (F∙∙∙F) interactions are the major driving forces in achieving hierarchical superstructures. The resulting bright red gels showed the presence of highly entangled three-dimensional networks and helical nanofibres with both (P and M) handednesses. The gels recover up to 87% of its original storage modulus even after several cycles under oscillatory step-strain rheological measurements showing rapid self-healing. The luminescent properties, along with thermo- and mechanoresponsive gelation open the potential to utilize synthetically simple discrete complexes in advanced optical materials.