Triplet conformation in chromophore-fused cyclooctatetraene dyes

Cyclooctatetraene (COT) has a tub-shaped conformation in its ground non-aromatic state, while it is predicted to have a planar aromatic triplet state. However, COT possesses a non-vertical triplet state and therefore its detection has remained elusive through direct photoexcitation. Recently, fluorescent dyes synthesized by fusing COT with anthracene and phenazine wings have shown a large Stokes shift implying a significant conformational change in their excited singlet manifold. Here, using broadband transient absorption spectroscopy supported with electronic structure calculations, we demonstrate that intersystem crossing occurs in the planar COT conformation in these flapping dyes. We confirm that such a planar conformation in the triplet state does not impart aromaticity to the COT backbone, as previously predicted. Our work therefore provides the basis for the requisite structural design principles that would allow for triplet formation from excited singlet states in COT-based functional molecules.

Automated summary

Fluorescent dyes synthesized by fusing COT with anthracene and phenazine wings exhibit a large Stokes shift, indicating significant conformational changes in their excited singlet states. Using broadband transient absorption spectroscopy and electronic structure calculations, we confirm intersystem crossing occurring in the planar COT conformation in these flapping dyes. We find that the planar conformation in the triplet state does not impart aromaticity to the COT backbone as previously predicted. This work provides the basis for designing COT-based functional molecules that can form triplets from excited singlet states.