Tris-benzo[cd]indole Cyanine Enables the NIR-photosensitized Radical and Thiol-ene Polymerizations at 940 nm.

A near-infrared-absorbing heptamethine (HM+) incorporating three bulky benzo[cd]indole heterocycles was designed to efficiently prevent self-aggregation of the dye, which results in a strong enhancement of its photoinitiating reactivity as compared to a parent bis-benzo[cd]indole heptamethine (HMCl+) used as a reference system. In this context, we highlight an efficient free-radical NIR-polymerization up to a 100% acrylates C=C bonds conversion even under air conditions. Such an important initiating performance was obtained by incorporating our NIR-sensitizer into a three-component system leading to its self-regeneration. This original photoredox cycle was thoroughly investigated through the identification of each intermediary species using EPR spectroscopy.