Photoinduced Dynamics of 13,13′-Diphenylpropyl-β-carotene

Carotenoids are ubiquitous pigment systems in nature which are relevant to a range of processes, such as photosynthesis, but the detailed influence of substitutions at the polyene backbone on their photophysics is still underexplored. Here, we present a detailed experimental and theoretical investigation of the carotenoid 13,13′-diphenylpropyl-β-carotene using ultrafast transient absorption spectroscopy and steady-state absorption experiments in n-hexane and n-hexadecane, complemented by DFT/TDDFT calculations. In spite of their bulkiness and their potential capability to “fold back” onto the polyene system, which could result in π-stacking effects, the phenylpropyl residues have only a minor impact on the photophysical properties compared with the parent compound β-carotene. Ultrafast spectroscopy finds lifetimes of 200–300 fs for the S(2) state and 8.3–9.5 ps for the S(1) state. Intramolecular vibrational redistribution with time constants in the range 0.6–1.4 ps is observed in terms of a spectral narrowing of the S(1) spectrum over time. We also find clear indications of the presence of vibrationally hot molecules in the ground electronic state (S(0)*). The DFT/TDDFT calculations confirm that the propyl spacer electronically decouples the phenyl and polyene π-systems and that the substituents in the 13 and 13′ positions point away from the polyene system.