Speciation and Photoluminescent Properties of a 2,6‐Bis(pyrrol‐2‐yl)pyridine in Three Protonation States

2,6‐Bis(pyrrol‐2‐yl)pyridines are important building blocks for supramolecular assemblies and photoluminescent main group and transition metal compounds. Sterically encumbered 2,6‐bis(5‐(2,4,6‐trimethylphenyl)‐3‐phenyl‐1H‐pyrrol‐2‐yl)pyridine, H2MesPDPPh, can adopt monomeric and dimeric structures in the solid state and in solution, controlled by competing inter‐ and intramolecular hydrogen bonds. Deprotonation in the presence of lithium cations provides Li2MesPDPPh, which can be isolated in monomeric and dimeric forms depending on solvent polarity. Protonation of H2MesPDPPh disrupts intramolecular hydrogen bonding and provides the monomeric pyridinium salt [H3MesPDPPh]Cl. Independent of solvent polarity, all three derivatives exhibit intense fluorescence in solution. The absorption and emission spectra are highly sensitive to the level of protonation, which can be rationalized by the effects of (de)protonation on the HOMO and LUMO of the tricyclic π‐system. Small proton, big impact: Three protonation states of a bulky 2,6‐bis(pyrrol‐2‐yl)pyridine were isolated and structurally characterized. Dimeric and monomeric species were identified depending on solvent polarity and hydrogen bonding capabilities. The photoluminescent properties are highly sensitive to the level of protonation, which attenuates the energies of the HOMO and LUMO.