Luminescence and Length Control in Nonchelated d8‐Metallosupramolecular Polymers through Metal‐Metal Interactions

Abstract Supramolecular polymers (SPs) of d8 transition metal complexes have received considerable attention by virtue of their rich photophysical properties arising from metal‐metal interactions. However, thus far, the molecular design is restricted to complexes with chelating ligands due to their advantageous preorganization and strong ligand fields. Herein, we demonstrate unique pathway‐controllable metal‐metal‐interactions and remarkable 3MMLCT luminescence in SPs of a non‐chelated PtII complex. Under kinetic control, self‐complementary bisamide H‐bonding motifs induce a rapid self‐assembly into non‐emissive H‐type aggregates (1A). However, under thermodynamic conditions, a more efficient ligand coplanarization leads to superiorly stabilized SP 1B with extended Pt⋅⋅⋅Pt interactions and remarkably long 3MMLCT luminescence (τ 77 K=0.26 ms). The metal‐metal interactions could be subsequently exploited to control the length of the emissive SPs using the seeded‐growth approach.