Room-Temperature Phosphorescence of Nicotinic Acid and Isonicotinic Acid: Efficient Intermolecular Hydrogen-Bond Interaction in Molecular Array.

Pure organic room-temperature phosphorescence (RTP) has attracted wide interest due to its unique advantages and promising applications. However, it is still challenging to develop efficient RTP through precise molecular design. In this work, RTP is observed from two simple aromatic acids, nicotinic acid (NA) and isonicotinic acid (INA), in the crystal state. Single crystal structure analysis indicates that an intense hydrogen bond between the pyridine nitrogen atom and the carboxyl group results in zigzag and linear molecular packing modes in NA and INA crystal. From theoretical calculations, the hydrogen bond can effectively promote the intersystem crossing process and stabilize triplet exciton. The identical molecular orientations in the molecular array contribute to the larger dipole moment of INA as compared to that of NA, which should be responsible for the red-shifted photoluminescence and RTP of INA. When the hydrogen bond is destructed by grinding or deprotonation, the RTP decreases sharply, further confirming the crucial role of the hydrogen bond on RTP.