Mediated Generation of Conjugate Acid by UV and Blue Sensitizers with Upconversion Nanoparticles at 980 nm.

NIR and UV exposure of systems comprising upconversion nanoparticles (UCNP) based on NaYF :Tm/Yb@NaYF , a sensitizer absorbing either in the blue or UV region, and an onium salt with weak coordinating anion resulted in formation of conjugate acid (con-H ). That was namely Ivocerin (di(4-methoxybenzoyl)diethylgermane), ITX (2-iso-propyl thioxanthone), anthracene, pyrene, rubrene, camphore quinone, and a strong fluorescent coumarin (1,1,6,6,8-pentamethyl-2,3,5,6-tetrahyhdro-1H,4H-11-oxa-3a-aza-benzo[de]anthracene-10-one). Quantification occurred by treatment with Rhodamine B lactone whose color switched to intensive red after photolytic formation of con-H .

NIR-Sensitized Activated Photoreaction between Cyanines and Oxime Esters: Free-Radical Photopolymerization.

Cyanines comprising either a benzo[e]- or benzo[c,d]indolium core facilitate initiation of radical photopolymerization combined with high power NIR-LED prototypes emitting at 805 nm, 860 nm, or 870 nm, while different oxime esters function as radical coinitiators. Radical photopolymerization followed an initiation mechanism based on the participation of excited states, requiring additional thermal energy to overcome an existing intrinsic activation barrier. Heat released by nonradiative deactivation of the sensitizer favored the system, even under conditions where a thermally activated photoinduced electron transfer controls the reaction protocol.