Two‐photon Clusteroluminescence Enabled by Through‐Space Conjugation for In Vivo Bioimaging

Clusteroluminescence (CL) materials without largely conjugated structures have gained significant attention due to their unique photophysical properties and potential in bioimaging. However, low luminescence efficiency and short emission wavelength limit their development. This work designs three luminogens with CL properties (CLgens) by introducing n‐electron‐involved through‐space conjugation (TSC) into diarylmethane. Apart from single‐photon excited long‐wavelength (688 nm) and high‐efficiency (29%) CL, two‐photon clusteroluminescence (TPCL) is successfully achieved in such small luminogens with only two isolated heteroatomic units. TSC stabilized in the aggregate state has been proven to realize efficient spatial electron delocalization similar to conventionally conjugated compounds. Encouraged by the excellent TPCL properties, two‐photon imaging of blood vessels in vivo and biocompatibility verification utilizing CLgens are also achieved. This work illustrates the essential role of TSC in promoting nonlinear optical properties of CLgens and may facilitate further design and development of the next generation of bioprobes with excellent biocompatibility.