Metal‐Metal‐π Interaction: A Pathway to Construct Organic–Inorganic Excited‐State and Supramolecular Assembly

Excited states arising from metal–metal (M–M) or π–π interactions play a foundational role in photochemistry and materials science, enabling applications in optoelectronics, photocatalysis, and beyond. However, the controlled integration of these two classic interaction motifs into a single, cooperative excited state remains unexplored. Herein, we report the design and realization of a hybrid excited state—designated as the [dσ*–π→π*] state—engineered through the synergistic combination of M–M and π–π interactions. This excited state is generated via directional orbital overlap between metal atoms and carbon materials in a supramolecular assembly. Detailed spectroscopic and computational studies confirm the delocalized nature of this excited state through the M–M–π interaction. The involvement of the heavy platinum atom imparts long‐lived triplet emission character, while the directional M–M–π orbital overlap gives rise to emergent photophysical properties, including strong emission polarization, exciton‐exciton annihilation, and exciton migration. This work establishes a new strategy for engineering excited states, opening avenues for developing advanced light‐harvesting and photo‐functional metal–organic hybrid materials.