Confinement of the Triplet States in π‐Conjugated BODIPY Dimers Linked with Ethynylene or Butadiynylene Bridges: A Different View on the Effect of Symmetry

Understanding the impact of theexcited state wavefunction confinement is crucial for the engineering of the photophysical properties andapplications of organic chromophores. In the present contribution, the localization of the triplet state wavefunctions of some symmetric ethyne / butadiyne bridged BODIPY dimers and asymmetric BODIPY derivatives presenting extended pi-conjugation frameworks is studied with time-resolved electron paramagnetic resonance spectroscopy and time-dependent density functional theory computations. Based on the Zero Field Splitting D parameters, we conclude that the triplet state wavefunctions are highly localizedon one BODIPYunit in the symmetric dimers, which is consistent with the ab initio modelling that finds delocalized triplet state destabilized by 12 - 14 kcal mol-1 as compared to its localized counterpart. The result provides a new insight into the study of triplet excited state confinement and the design of molecular wires or photosensitizers for photovoltaics and photocatalysis.