Temperature influence on the energy of nonspecific and specific interactions taking place between 4-aminophthalimide (4-AP) and homogeneous solvents.

Temperature induced spectral shifts of the 4-aminophthalimide (4-AP) emission spectra have been measured and compared to the predictions of the McRae solvent induced shift theory (J. Phys. Chem., 1957, 61, 562-572). Three moderately polar chloroalkanes selected as nonspecifically interacting media, and six hydrogen accepting or/and electron pair donating solvents have been used as the media in which the temperature influence on 4-AP-solvent interactions has been studied in the range of 180-320 K. Using the ab initio determined 4-AP ground state dipole moment and fitting appropriate expression originating from the mentioned theory to the shifts found in the chloroalkanes it has been possible to estimate the 4-AP excited state dipole moment, the probe excited state Onsager radius and its gas phase emission spectrum position. Using these values the thermochromic shifts of 4-AP emission spectra in hydrogen bond forming solvents have been predicted and compared to the experimental one. Temperature has been found to have different impact on the changes, upon excitation of the probe, in the mean values of the energies of different hydrogen bonds formed by 4-AP with solvents molecules.