Metallomacrocyclic Ligands Stabilized Icosahedral Superatomic Nanoclusters With NIR‐I to NIR‐II Phosphorescence Modulation

ABSTRACT

Coinage metal nanoclusters with near‐infrared‐II (NIR‐II, λ _PL > 1000 nm) photoluminescence hold great promise for biological applications. Here, we report the first icosahedral M ₁₃ cluster exhibiting NIR‐II phosphorescence, achieved through an unprecedented metallomacrocyclic ligand coordination combined with an alloying strategy, denoted as M ₁₃ @M ₆ clusters. The metallomacrocyclic ligands strongly regulate the photophysical properties of the M ₁₃ core, governing its lowest triplet excited state (T ₁ ) and enabling a markedly red‐shifted emission. They also provide a distinctive “core surface→metallomacrocycle→inner core” pathway for stepwise silver doping. Combined theoretical calculations and emission spectra reveal that doping‐induced charge transfer between the M ₁₃ core and M ₆ metallomacrocycles drives the photoluminescence shift from the NIR‐I to the NIR‐II region. Furthermore, functionalization of the metallomacrocyclic ligands with bulky pyrene groups enhances NIR‐II emission by an order of magnitude. Catalytic studies demonstrate that site‐specific tuning of metal composition within M ₁₃ @M ₆ clusters enables nanometer‐scale modulation of catalytic activity, highlighting the versatility of metallomacrocyclic ligands for regulating both luminescence and catalytic properties. This work not only extends coinage metal cluster protection from conventional organic ligands to metallomacrocycles but also provides a systematic framework for NIR‐II emission modulation through inner‐core and metallomacrocycle doping, ligand engineering at the coordination interface, and outer‐sphere functionalization.