π-Bridge Effect on Symmetric Carbazole-Based Small Molecules for Realizing Ultraviolet Fluorescent Emission.

A series of symmetric carbazole derivatives (CzP-H, CzP-CN, CzP-Me, and CzP-OMe), which comprise electron-donating and electron-drawing groups appending on a phenyl core, was synthesized and characterized in detail. These compounds exhibit excellent thermal stabilities, with thermal decomposition temperatures exceeding 400 °C. From the fluorescent spectra in film, CzP-H, CzP-Me, and CzP-OMe showed UV to blue-violet emission, with peaks at 396 nm, 402 nm, and 392 nm, respectively. The energies of CzP-H, CzP-CN, CzP-Me, and CzP-OMe were 3.39 eV, 2.83 eV, 3.50 eV, and 3.35 eV, respectively. From the electrochemical measurements, the highest occupied molecular orbital (HOMOs) energy levels were −5.30 eV, −5.64 eV, −5.46 eV, and −5.24 eV for CzP-H, CzP-CN, CzP-Me, and CzP-OMe, respectively. Through calculations from HOMO energy levels and energies, the lowest unoccupied molecular orbital (LUMOs) energy levels of CzP-H, CzP-CN, CzP-Me, and CzP-OMe were −1.91 eV, −2.81 eV, −1.96 eV, and −1.89 eV, respectively. Therefore, the introduction of different substitutes in phenyl cores would distinctly affect the photophysical properties. These results indicate that the prepared carbazole derivatives could be potential candidates for realizing ultraviolet or blue-violet emission.