Unveiling the dual-state emissive behaviour of 4,6-diarylpyrimidin-2-amines through a plug-and-play approach

Abstract

Abstract We present here a series of 4,6-diarylpyrimidin-2-amine derivatives (5a-j) with tunable optical properties both in the solid and solution states. Our plug-and-play fluorophore design demonstrates that the aryl groups at the 4th and 6th positions of the 2-aminopyrimidine core enable distinct optical characteristics for each derivative. The fluorophore design concept was validated using theoretical and spectroscopic methods. The designed compounds were synthesised in moderate to good yields, and their structures were confirmed via IR, NMR, HRMS, and single-crystal XRD analyses. Optical studies revealed that varying the aryl substituents significantly impacts absorption, emission, and bandgap values in both phases. The absolute quantum yields (ϕF) of the synthesised derivatives ranged from 8.11 to 71.00% in DMF and 5.86–29.43% in thin films, with fluorescence lifetimes (τ) between 0.8 and 1.5 ns in DMF and 0.63–3.16 ns in films, respectively. CIE (Commission Internationale de l’Éclairage) diagrams indicate blue-green emission for 5a-j in the visible spectrum. The electrochemical analysis confirmed that the HOMO/LUMO (Highest Occupied Molecular Orbital/Lowest Unoccupied Molecular Orbital) energy levels can be modulated by altering the substituent rings. These results highlight the dual-state emission properties of 2-aminopyrimidine fluorophores, demonstrating their potential for a wide range of optoelectronic and advanced applications.

Keywords

• CIE
• Fluorophores
• HOMO-LUMO
• Optical bandgap
• 2-aminopyrimidine
• 4, 6-diarylpyrimidin-2-amine