The Metal–Metal‐to‐Ligand Charge Transfer Excited State and Supramolecular Polymerization of Luminescent Pincer PdII–Isocyanide Complexes

Pincer Pd II –isocyanide complexes are described that display intermolecular interactions and emissive 3 MMLCT excited states in aggregation state(s) at room temperature. The intermolecular Pd II −Pd II and ligand–ligand interactions drive these complexes to undergo supramolecular polymerization in a living manner. Comprehensive spectroscopic studies reveal a pathway with a kinetic trap that can be modulated by changing the counteranion and metal atom. The Pd II supramolecular assemblies comprise two different aggregation forms with only one to be emissive. DFT/TDDFT calculations lend support to the MMLCT absorption and emission of these pincer Pd II –isocyanide aggregates.