The deexcitation of the S₁ state of aminoanthraquinones: a steadystate and timeresolved study

Abstract

The non-radiative processes of deactivation from the lowest singlet excited state of aminoanthraquinones have been studied using steady-state and time-resolved methods. The fluorescence decay rate constant, k_f correlates well with the solvent polarity parameter, E_T(30), in nonhydrogen bonding solvents. Large deuterium isotope effects in fluorescence lifetimes (τ_f) and quantum yields (Φ_f) are observed in the case of 1-amino (AAQ) and 1-methylaminoanthraquinones (MAQ), where the S₁ state is mainly deactivated through internal conversion to the ground state. The temperature-dependence of the fluorescence quantum yields of various aminoanthraquinones was also investigated. The Φ_f and τ_f exhibited strong temperature-dependence in the case of 1-acetylaminoanthraquinone (ACAQ). In the case of ACAQ, the intersystem crossing to the triplet state is a major deactivation channel from the S₁ and in this derivative a close-lying T₂ state seems to be responsible for the high k_isc rate. The fluorescence properties of 1,5-diaminoanthraquinone (DAQ) are affected by intermolecular hydrogen bonding with alcohols. Increasingn-alkyl chain length in the case of l-(n-alkyl)aminoanthraquinones from methyl to butyl does not produce any change in the fluorescence properties, whereas a hydroxypropyl substitution results in a small decrease of Φ_f and τ_f in these compounds, indicating an interaction of the hydroxyl group with the carbonyl group of the aminoanthraquinones.