Abstract
With 4-fluoro-N,N-dimethylaniline (DMA4F), only a single fluorescence from a locally excited (LE) state is observed, irrespective of solvent polarity, temperature, and excitation wavelength. The relatively small excited state dipole moment mu(e) = 7.3 D confirms the identification as LE. The single exponential fluorescence decays in the nonpolar n-hexane (2.04 ns) and in the strongly polar acetonitrile (5.73 ns) are a further support. Similar results are obtained with 4chloro-N,N-dimethylaniline (DMA4C1), having a chlorobenzene subgroup, a somewhat better electron acceptor than the fluorobenzene moiety in DMA4F. The absence of intra-molecular charge transfer (ICT) with DMA4F is in accord with its large energy gap Delta E(S-1,S-2) of 8300 cm-(1) in n-hexane between the two lowest singlet excited states, which is even larger than that (6300 cm(-1)) of N,N-dirnethylaniline (DMA), for which an LE -> ICT, reaction likewise does not occur. The results with DMA4F are in contradiction with a publication by Fujiwara et al. (Chem. Phys. Lett. 2013, 586, 70), in which the appearance of dual LE + ICT emission is reported for DMA4F in n-hexane and MeCN at room temperature. The ICT/LE fluorescence quantum yield ratio Phi/(ICT)/Phi(LE) reached a maximum value of similar to 2in- n-hexane and surprisingly also in MeCN, as the excitation wavelength approaches the red-edge of the absorption spectrum. These, in our opinion, erroneous observations were supported by time-dependent density functional theory (TDDFT) calculations, which compute a perpendicularly twisted lowest ICT state (TICT) state. This is a further example of the general tendency, of computations to find a TICT conformation for the lowest excited singlet state of electron donor/acceptor molecules such as p-substituted anilines.
