Intramolecular Long-Range Charge-Transfer Emission in Donor–Bridge–Acceptor Systems

Charge recombination to the electronic ground state typically occurs nonradiatively. We report a rational design of donor–bridge–acceptor molecules that exhibit charge-transfer (CT) emission through conjugated bridges over distances of up to 24 Å. The emission is enhanced by intensity borrowing and extends into the near-IR region. Efficient charge recombination to the initial excited state results in recombination fluorescence. We have established the identity of CT emission by solvent dependence, sensitivity to temperature, femtosecond transient absorption spectroscopy, and unique emission polarization patterns. Large excited-state electronic couplings and small energy gaps enable the observation of intramolecular long-range CT emission over the unprecedented long distance. These results open new possibilities of using intramolecular long-range CT emission in molecular electronic and biomedical imaging probe applications.