Distance Dependence of Electron Spin Polarization during Photophysical Quenching of Excited Naphthalene by TEMPO Radical

Quenching of excited states by a free radical is generally studied in systems where these two are separate entities freely moving in a liquid solution. Random diffusive encounters bring them together to cause the quenching and leave the spins of the radical polarized. In the dynamics of the radical–triplet pair mechanism of the generation of electron spin polarization (ESP), the distance-dependent exchange interaction plays a crucial role. To investigate how the distance between the excited molecule and the radical influences the ESP, we have covalently linked a naphthalene moiety to a TEMPO free radical through a spacer group of three different lengths. We compared the ESP process of these linked compounds with that of the usual “unlinked system” of naphthalene and TEMPO through time-resolved EPR experiments at low temperature in <i>n</i>-hexane solution. The time evolution of both the linked and the “unlinked system” was treated on a similar footing. The time-dependent EPR signal was analyzed by combining photophysical kinetics and time-dependent Bloch equations incorporating spin dynamics. Sequential quenching of the singlet state and the triplet state of naphthalene was seen in all the systems, as revealed through the spin-polarized TREPR spectra of opposite phase. The magnitudes of the ESP in the linked molecules were higher than those of the “unlinked system,” showing that when the two moieties are held together greater mixing of quartet–doublet states takes place. The magnitudes of ESP steadily decrease with increasing the length of the spacer group. The polarization magnitudes due to triplet quenching and singlet quenching are very similar, differing by a factor of only ∼2. These characteristics show that for all the linked molecules the quenching takes place in the “weak exchange” regime and at almost the same distance of separation between the two moieties. Our results also showed that observation of small absorptive TREPR signals does not necessarily imply that its magnitude of polarization is small