A Straightforward Synthesis and Structure–Activity Relationship of Highly Efficient Initiators for Two-Photon Polymerization

The development of practical two-photon absorption photoinitiators (TPA PIs) has been slow due to their complicated syntheses often reliant on expensive catalysts. These shortcomings have been a critical obstruction for further advances in the promising field of two-photon-induced photopolymerization (TPIP) technology. This paper describes a series of linear and cyclic benzylidene ketone-based two-photon initiators containing double bonds and dialkylamino groups synthesized in one step via classical aldol condensation reactions. Systematic investigations of structure–activity relationships were conducted via quantum-chemical calculations and experimental tests. These results showed that the size of the central ring significantly affected the excited state energetics and emission quantum yields as well as the two-photon initiation efficiency. In the TPIP tests the 4-methylcyclohexanone-based initiator displayed much broader ideal processing windows than its counterparts with a central five-membered ring and previously described highly active TPA PIs. Surprisingly, a writing speed as high as 80 mm/s was obtained for the microfabrication of complex 3D structures employing acrylate-based formulations. These highly active TPA PIs also exhibit excellent thermal stability and remain inert to one-photon excitation. Straightforward synthesis combined with high TPA initiation efficiency makes these novel initiators promising candidates for commercialization.