Abstract
The rate constants of intramolecular double hydrogen transfer have been determined for of tert-butyl-substituted porphycenes: 2-tert-butyl-, 2,7-di-tert-butyl-, 2,7,12-tri-tert-butyl-, and 2,7,12,17-tetra-tert-butylporphycene using femtosecond pump-probe polarization spectroscopy. The rates increase monotonically with the number of substituents. As is the case for other porphycenes studied so far, the tautomerization becomes slower after excitation to the lowest excited singlet state. The potential for the trans-trans self-exchange reaction is symmetrical in di- and tetra-tert-butyl substituted derivatives, but not for the singly and triply substituted ones. Our studies enabled determination of the relative populations of nonequivalent tautomers and thus of the equilibrium constants in S0 and S1 states, as well as estimation of ground and excited state activation energies for the tautomerization process.
© by Oldenbourg Wissenschaftsverlag, München, Germany
