Effect of Bridging Position on the Two-Photon Polymerization Initiating Efficiencies of Novel Coumarin/Benzylidene Cyclopentanone Dyes

One- and two-photon photophysical and photochemical properties of dyes 3-DAC and 4-DAC containing coumarin and benzylidene cyclopentanone moieties were studied. Their ground state configurations were optimized using both Hartree−Fock and density functional theory (B3LYP functional) methods, and excited-state properties were calculated using time-dependent density functional theory. These two dyes share the same formula and possess similar structures, except for different bridging positions between the benzylidene cyclopentanone and coumarin moieties. The bridging position was found to have a significant effect on the electronic structure and photophysical and photochemical properties of the dyes. 3-DAC shows higher conjugation and is more planar than 4-DAC, and it exhibits a larger TPA cross section. In contrast, 4-DAC has a twisted conformation, exhibits a lower electron transfer free energy with initiator and shows higher sensitizing efficiencies in one-photon polymerization. Furthermore, the applicatio...