Unusual Through‐Space Interactions between Oxygen Atoms that Mediate Inverse Morphochromism of an AIE Luminogen

Abstract We have studied the photophysics of tetrafurylethene, an aggregation‐induced emission luminogen with exceptionally short intramolecular O−O distances of 2.80 Å and a significant red‐shifted morphochromism (27 nm) when going from the aggregate to the crystal. The short O−O distances, which are substantially smaller than the sum of the van der Waals radii (3.04 Å), are due to the fact that the oxygen atoms act as an electronic bridge connecting the furan rings on opposite ends of the central double bond, giving rise to a circular delocalization of the π‐electron density across the rings. In the excited state the O−O distance is further reduced to 2.70 Å; the increased O−O interaction causes a narrowing of the HOMO–LUMO gap, resulting in the red morphochromism of the emission. Our results show the structural origin of the red‐shifted emission lies in close O−O contacts, paving the way for understanding the clusteroluminescence of oxygen‐rich non‐conjugated systems that emit visible light.