Millisecond Time-scale Photoluminescence of B–N-doped Tetrathienonaphthalene with Borane/Amine Substituents

BN-doped polycyclic aromatic hydrocarbons (PAHs) have attracted numerous attentions because of their fascinating optical and electronic properties. In this work, a series of electron-donor (amine)- and -acceptor (borane)-functionalized BN-doped polycyclic aromatic hydrocarbons were prepared to study the substituents’ effect on the photophysical properties. As a result, the compound with both donor and acceptor, BN, exhibits both local emission (LE) and charge-transfer emission (CT) in polar solvents. Especially, the CT emission with a longer wavelength revealed a lifetime as long as millisecond time scale at room temperature, indicating typical phosphorescence characteristics. Low-temperature photoluminescent (PL) spectroscopy and a theoretical study were conducted to help to interpret this phenomenon, and it turned out to be the lowering of the S 1 energy level of BN which makes the intersystem crossing favorable. Furthermore, fluoride anion titration experiments exhibit the application potential of the dual-emission phenomenon of BN for ratiometric sensory materials.