Femtosecond broadband time-resolved fluorescence and transient absorption study of the intramolecular charge transfer state of methyl 4-dimethylaminobenzoate.

A combined application of femtosecond broadband time-resolved fluorescence (fs-TRF), fluorescence anisotropy (fs-TRFA) and fs to microsecond (μs) transient absorption (TA) have been used to probe directly the dynamics, nature, formation and decay paths of the singlet intramolecular charge transfer (1ICT) state of methyl 4-dimethylaminobenzoate (1a) in acetonitrile. The result reveals explicit evidence for a common electronic origin (the Lanature) of the 1ICT state and its precursor the locally excited (1LE) state to account jointly for the dual florescence known to this system. It also shows that the ICT reaction from the 1LE to 1ICT state occurs with time constant of ∼0.8 ps and the 1ICT state formed decays with a ∼1.9 ns time constant leading mainly to a ππ* natured triplet state (3T1). The 3T1then relaxes with a ∼4 μs lifetime under deoxygenated condition resulting in full recovery of the ground state (S0). As a case study, this work contributes novel experimental data for improved understanding of the mechanism of ICT reaction; it also reveals a distinct deactivation pattern for this prototype para-amino substituted aromatic carbonyl compound in acetonitrile. [ABSTRACT FROM AUTHOR]

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