Two new twisted intramolecular charge transfer (TICT) donor-p-acceptor compounds were designed bycombining a well-known electron acceptor naphthalimide unit with a classic electron donordimethylaniline through two types of different rigid linkers. The combined steady-state and timeresolved spectroscopy of molecules in solvents of different polarities in comparison to solid-statesolvation experiments of doped polymer matrixes of different polarities allowed distinguishing betweensolvation and conformation determined processes. The photophysical measurements revealed that nonpolar solutions possess high fluorescence quantum yields of up to 70% which is a property of pretwisted/planar molecules in the excited charge transfer (CT) states. The increase of polarity allows tuningthe Stokes shift through all the visible wavelength range up to 8601 cmÿ1 which is accompanied by athree orders of magnitude drop of fluorescence quantum yields. This is a result of the emerged TICTstates as dimethylaniline twists to a perpendicular position against the naphthalimide core. The TICTreaction of molecules enables an additional non-radiative excitation decay channel, which is not presentif the twisting is forbidden in a rigid polymer matrix. Transient absorption spectroscopy was employed tovisualize the excited state dynamics and to obtain the excited state reaction constants, revealing thatTICT may occur from both the Franck-Condon region and the solvated pre-twisted/planar CT states.Both molecules undergo the same photophysical processes, however, a longer linker and thus a higherexcited state dipole moment determines the faster excited state reactions< Réduire