Three new [Ru(bpy)2X]+ complex ions, where bpy represents bipyridyl ligand and X denotes pH-sensitive pyridyl diazolate or pyrazinyl diazolate coordination site, have been computationally designed and synthesised as pH sensitive molecules. The choice of pyridyl and pyrazinyl moieties allows for the nitrogen content to vary, while the influence of the protonation site is quantified by using 1,2-diazolate and 1,3-diazolate derivatives. The absorption and emission properties of the deprotonated and protonated complex ions were characterised by UV-vis and photoluminescence spectroscopy, as well as by time-dependent density functional theory. Protonation causes (1) a strong blue shift in the lowest energy 3MLCT→S0 emission wavelengths, (2) a substantial increase in the emission intensity and (3) a change in the character of the corresponding 3MLCT emitting states. The blue shift in the emission wavelength becomes less pronounced when the nitrogen content in the X ligand increases and when going from 1,2- to 1,3-azolate derivatives. The contrast in the emission intensity of the protonated/deprotonated forms is highest for the complex ion, containing 2-pyridyl derivative of the 1,2-diazolate. The complex ions are suggested as potential pH-responsive materials based on change in the colour and intensity of the emitted radiation. The broad impact of the research is that demonstrate that the modification of the nitrogen content and position within the protonable ligands is an effective approach for modulation of the pH-optosensing properties of Ru-polypyridyl complexes.
This research output has an Altmetric Attention Score of 2. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 04 June 2019.
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