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

Square planar platinum(II) complexes are attractive building blocks for multifunctional soft materials due totheir unique optoelectronic properties. However, for soft materials derived from synthetically simple discretemetal complexes, achieving a combination of optical properties, thermoresponsiveness and excellentmechanical properties is a major challenge. Here, we report the rapid self-recovery of luminescent metallogelsderived from platinum(II) complexes of perfluoroalkyl and alkyl derivatives of terpyridine ligands. Using singlecrystal X-ray diffraction studies, we show that the presence of synergistic platinum–platinum (PtPt) metallo-polymerization and fluorine–fluorine (FF) interactions are the major drivingforces in achieving hierarchicalsuperstructures. The resulting bright red gels showedthe presence of highly entangled three-dimensionalnetworks and helical nanofibres with both (PandM) handedness. The gels recoverupto87%oftheiroriginalstorage modulus even after several cycles under oscillatory step-strain rheological measurements showingrapid self-healing. The luminescence properties, along with thermo- and mechanoresponsive gelation,provide the potential to utilize synthetically simplediscrete complexes in advanced optical materials.Peer reviewe