Two-Photon Initiating Efficiency of a Ditopic Alkoxynitrostilbene Reacting through a Self-Regenerative Mechanism

The photophysical properties and the photoinitiating reactivity of a ditopic alkoxynitrostilbene were compared to those of its single branch chromophore used as a reference. Whereas a trivial additive effect is observed when considering the one- and two-photon absorption properties, a clear and very significant amplification has been highlighted for the photoreactivity of this free radical photoinitiator which was used as a hydrogen abstractor in presence of an aliphatic amine co-reactant. We indeed demonstrate that the proximity of two nitroaromatics moieties within the same molecular architecture gives rise to an original cycling mechanism based on a stepwise photo triggering of each photoredox center followed by a subsequent regenerative process. The combination of a high two-photon absorption cross-section (δ780nm ≈330 GM) with a strong enhancement in photoreactivity makes this nitrostilbene bichromophore a very suitable candidate for two-photon polymerization applications.