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

Von Wiley-VCH zur Verfügung gestellt

The supramolecular polymerization of a PtII complex with a monodentate ligand design based on self-complementary H-bonding initially affords a non-luminescent supramolecular polymer (SP). Pathway control then enables a consecutive transformation to an SP exhibiting close Pt⋅⋅⋅Pt contacts with long-lived 3MMLCT emission. Apart from luminescence, the Pt⋅⋅⋅Pt-interactions also enable control over the size of the self-assembled nanostructures.


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.

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