Two-dimensional electronic spectroscopy reveals how selective Q-band excitation influences exciton dynamics in porphyrin aggregates, suggesting design improvements for materials.
High Resolution Image Download MS PowerPoint Slide The ultrafast photophysics of the Q-band manifold of tetra( p -sulfonatophenyl)porphyrin (H 2 TPPS) is investigated by two-dimensional electronic spectroscopy (2DES) in both its monomeric and J-aggregated forms. By selectively exciting different regions of the Q bands, we uncover strongly excitation-dependent relaxation dynamics in the aggregates. Photoexcitation centered on the lower-energy Q transition leads to pronounced interband coupling and clear signatures of exciton–exciton annihilation, whereas selective excitation of the higher-energy side of the Q-band manifold limits annihilation. These findings provide new insight into how the mixed Q-band structure governs excitation flow in porphyrin aggregates and open avenues for the rational design of materials with tailored annihilation properties.
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Cherchi et al. (2026) studied this question.
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