Two- and three-photon processes during photopolymerization in 3D laser printing.

The performance of a photoinitiator is key to control efficiency and resolution in 3D laser nanoprinting. Upon light absorption, a cascade of competing photophysical processes leads to photochemical reactions toward radical formation that initiates free radical polymerization (FRP). Here, we investigate 7-diethylamino-3-thenoylcoumarin (DETC), belonging to an efficient and frequently used class of photoinitiators in 3D laser printing, and explain the molecular bases of FRP initiation upon DETC photoactivation. Depending on the presence of a co-initiator, DETC causes radical generation either upon two-photon- or three-photon excitation, but the mechanism for these processes is not well understood so far. Here, we show that the unique three-photon based radical formation by DETC, in the absence of a co-initiator, results from its excitation to highly excited triplet states. They allow a hydrogen-atom transfer reaction from the pentaerythritol triacrylate (PETA) monomer to DETC, enabling the formation of the reactive PETA alkyl radical, which initiates FRP. The formation of active DETC radicals is demonstrated to be less spontaneous. In contrast, photoinitiation in the presence of an onium salt co-initiator proceeds intermolecular electron transfer after the photosensitization of the photoinitiator to the lowest triplet excited state. Our quantum mechanical calculations demonstrate photophysical processes upon the multiphoton activation of DETC and explain different reactions for the radical formation upon DETC photoactivation. This investigation for the first time describes possible pathways of FRP initiation in 3D laser nanoprinting and permits further rational design of efficient photoinitiators to increase the speed and sensitivity of 3D laser nanoprinting.