Six pyrimidine‐based push–pull systems substituted at positions C2 and C4/6 with phenylacridan and styryl moieties, employing methoxy or N,N‐diphenylamino donors, have been designed and synthesized through cross‐coupling and Knoevenagel reactions. X‐ray analysis confirmed that the molecular structure featured the acridan moiety arranged perpendicularly to the residual π system. Photophysical studies revealed significant differences between the methoxy and N,N‐diphenylamino chromophores. Solvatochromic studies revealed that the methoxy derivatives showed dual emission in polar solvents. Time‐resolved spectroscopy revealed that the higher energy band involved very fast (<80 ps) fluorescence, whereas the lower energy one included long components (≈30 ns) due to long‐lived intramolecular charge‐transfer fluorescence. In contrast to N,N‐diphenylamino chromophores, the methoxy derivatives also showed aggregation‐induced emission in mixtures of THF/water, as well as dual emission in thin films, covering almost the whole visible spectrum with corresponding chromaticity coordinates not far from that of pure white light. These properties render the methoxy derivatives as very promising organic materials for white organic light‐emitting diodes.

Highlights  The protonation effect on the excited state dynamics is investigated  Two pyrimidine chromophores, bearing the A-(π-D)2 and A-(π-D)3 structure, are used  Time resolved fluorescence spectroscopy (fs and ns) is employed  Protonation using three different acids, CSA, TFA and AcOH is studied  The dynamics of the neutral chromophores become faster upon protonation with AcOH

The initial anisotropy of asymmetrically substituted tri-podal compounds is greatly dependent on the excitation wavelength indicating that the molecule behaves as pseudo-octupolar (λexc = 380 nm) or dipolar (λexc = 400 nm).