Solvent-polarity dependence of ultrafast excited-state dynamics of -4-nitrostilbene.

Ultrafast excited-state dynamics of the simplest nitrostilbenes, namely -4-nitrostilbene (-NSB), was studied in solvents of various polarities with ultrafast broadband time-resolved fluorescence and transient absorption spectroscopies, and by quantum-chemical computations. The results revealed that the initially excited S(ππ*) state deactivation dynamics is strongly influenced by the solvent polarity. Specifically, the -NSB S-state lifetime decreases by three orders of magnitude from ∼60 ps in high-polarity solvents to ∼60 fs in nonpolar solvents. The strong solvent-polarity dependence arises from the differences in dipole moments among the S and relevant states, including the major intersystem crossing (ISC) receiver triplet states, and therefore, the solvent polarity can modulate their relative energies and ISC rates. In nonpolar solvents, the sub-100 fs lifetime is due to a combination of efficient ISC and internal conversion. In medium-polarity solvents, the S-state population decays a competing ISC relaxation mechanism in a biphasic manner, and the ISC rates are found to obey the inverse energy gap law of the strong coupling case. In high-polarity solvents, the S state is stabilized to a much lower energy such that ISC becomes energetically infeasible, and the S state decays barrier crossing along the torsion angle of the central ethylenic bond to the nonfluorescent perpendicular configuration. Regardless of the initial S-state deactivation pathways in various solvents, the excited-state population is ultimately trapped in the metastable T-state perpendicular configuration, at which a slower ISC occurs to bring the system to the ground state and bifurcate into either or form of NSB.