Excited-State Dynamics
of Monomeric and Aggregated
Carotenoid 8′-Apo-β-carotenal
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Abstract
Excited-state properties of monomeric and aggregated
carbonyl carotenoid
8′-apo-β-carotenal were studied by means of femtosecond
transient absorption spectroscopy. For monomers, the polarity-dependent
behavior characteristic of carotenoids with conjugated carbonyl group
was observed. In <i>n</i>-hexane the S<sub>1</sub> lifetime
is 25 ps, but it is shortened to 8 ps in methanol. This shortening
is accompanied by the appearance of new spectral bands in transient
absorption spectrum. On the basis of analysis of the transient absorption
spectra of monomeric 8′-apo-β-carotenal in <i>n</i>-hexane and methanol, we propose that the polarity-induced spectral
bands are due to the S<sub>1</sub>(A<sub>g</sub><sup>–</sup>)–S<sub>3</sub>(A<sub>g</sub><sup>+</sup>) transition, which
is enhanced upon breaking the symmetry of the molecule. This symmetry
breaking is caused by the conjugated carbonyl group; it is much stronger
in polar solvents where the S<sub>1</sub> state gains significant
charge-transfer character. Upon addition of water to methanol solution
of 8′-apo-β-carotenal we observed formation of aggregates
characterized by either blue-shifted (H-aggregate) or red-shifted
(J-aggregate) absorption spectrum. Both aggregate types exhibit excited-state
dynamics significantly different from those of monomeric 8′-apo-β-carotenal.
The lifetime of the relaxed S<sub>1</sub> state is 20 and 40 ps for
the H- and J-aggregates, respectively. In contrast to monomers, aggregation
promotes formation of triplet state, most likely by homofission occurring
between tightly packed molecules within the aggregate