Tuning ESIPT-coupled luminescence by expanding π-conjugation of a proton acceptor moiety in ESIPT-capable zinc(II)...

The emission of ESIPT-fluorophores is known to be sensitive to various external and internal stimuli and can be fine-tuned through substitution in the proton-donating and proton-accepting groups. The incorporation of metal ions in the molecules of ESIPT fluorophores without their deprotonation is an emerging area of research in coordination chemistry which provides chemists with a new factor affecting the ESIPT reaction and ESIPT-coupled luminescence. In this paper we present 1-hydroxy-5-methyl-4-(pyridin-2-yl)-2-(quinolin-2-yl)-1H-imidazole (HLq) as a new ESIPT-capable ligand. Due to the spatial separation of metal binding and ESIPT sites this ligand can coordinate metal ions without being deprotonated. The reactions of ZnHal₂ with HLq afford ESIPT-capable [Zn(HLq)Hal2] (Hal = Cl, Br, I) complexes. In the solid state HLq and [Zn(HLq)Hal2] luminesce in the orange region (λ_max = 600-650 nm). The coordination of HLq by Zn²⁺ ions leads to the increase in the photoluminescence quantum yield due to the chelation-enhanced fluorescence effect. The ESIPT process is barrierless in the S₁ state, leading to the only possible fluorescence channel in the tautomeric form (T), S₁^T → S₀^T. The emission of [Zn(HLq)Hal2] in the solid state is blue-shifted as compared with HLq due to the stabilization of the ground state and destabilization of the excited state. In CH₂Cl₂ solutions, the compounds demonstrate dual emission in the UV (λ_max = 358 nm) and green (λ_max = 530 nm) regions. This dual emission is associated with two radiative deactivation channels in the normal (N) and tautomeric (T) forms, S₁^N → S₀^N and S₁^T → S₀^T, originating from two minima on the excited state potential energy surfaces. High energy barriers for the GSIPT process allow the trapping of molecules in the minimum of the tautomeric form, S₀^T, resulting in the possibility of the S₀^T → S₁^T photoexcitation and extraordinarily small Stokes shifts in the solid state. Finally, the π-system of quinolin-2-yl group facilitates the delocalization of the positive charge in the proton-accepting part of the molecule and promotes the ESIPT reaction.