The Critical Role of nπ* States in the Photophysics and Thermally Activated Delayed Fluorescence of Spiro Acridine-Anthracenone

[Image: see text] The molecular photophysics and thermally activated delayed fluorescence (TADF) in spiro compounds are distinct because of the rigid orthogonal C–C bridging bond between donor and acceptor. The photophysics is found to be highly complex, with unprecedented multiple anti-Kasha emissions from three different singlet states, two of which are one-photon forbidden. The TADF mechanism is critically controlled by local acceptor nπ* states; the singlet nπ* state undergoes rapid intersystem crossing populating an energetically close acceptor ππ* triplet state. The acceptor triplet nπ* state couples nonadiabatically to a CT triplet state mediating reverse intersystem crossing. When the nπ* and CT states are energetically close, TADF is greatly enhanced with rISC rate reaching 10(7) s(–1). We observe neither DF from the singlet nπ* state nor electron transfer (ET) to form the (1)CT because there is no ET driving force; however, ET from the higher-energy donor singlet ππ* state readily occurs along with donor emission.