Design of Green-Emitting Salts from Substituted Pyridines: Understanding the Solid-State Photodimerization of trans-1,2-bis(4-pyridyl)ethylene

Polymorphic salts of trans-1,2-bis(4-pyridyl)ethylene (bpe), 2[bpeH₂ ] ⋅ (SO₄ )(2HSO₄ ) (1) and [bpeH₂ ] ⋅ 2HSO₄ (2) have been synthesized and their structures determined by X-ray crystallography. The Schmidt postulate predicts that neither of the salts will give rise to photodimerization so they can both potentially be applied as green light emitters. Despite the predictions, 1 undergoes a stereospecific solid-state photodimerization reaction with 100 % yield. This is due to UV induced combination of sliding and pedal-like movement of the pyridyl ring system that influences the alignment of C=C bonds. The sliding motion is restricted in 2. Consequently, the green emission from 1 is completely quenched after photodimerization. It is evident that counter ions play a dominant role in dis- and enabling photodimerization; their degree of protonization and lattice placement are important solvent controlled design parameters towards crystal structures that can act as future light emitters.