Synthesis of fully fused π‐conjugated cycloarenes embedded nonbenzenoid aromatics is challenging. In this work, the first example of four‐membered ring‐embedded cycloarene (MF2) was designed and synthesized in single‐crystal form by macrocyclization and ring fusion strategies. For comparison, single bond‐linked chiral macrocycle MS2 without two fused four‐membered rings and its linear‐shaped polycyclic benzenoid monomer L1 were also synthesized. The pronounced anti‐aromaticity of four‐membered rings significantly adjusts the electronic structures and photophysical properties of cycloarene, resulting in an enhancement of the photoluminescence quantum yield (PLQY) from 10.66% and 10.74% for L1 and MS2, respectively, to 54.05% for MF2, which is the highest PLQY among the reported cycloarenes. Notably, owing to the embedded four‐membered rings that reduce structural displacements, MF2 exhibits an ultra‐narrowband emission with a single‐digit full‐width at half‐maximum (FWHM) of only 7 nm (0.038 eV), which sets a new record among all reported organic narrowband luminescent molecules, and represents the first example of ultra‐narrowband emission in conventional polycyclic aromatic hydrocarbons (PAHs) devoid of heteroatoms.

Four‐Membered Ring‐Embedded Cycloarene Enabling Anti‐Aromaticity and Ultra‐Narrowband Emission