title: Effect of bridging position on the two-photon polymerization initiating efficiencies of novel coumarin/benzylidene cyclopentanone dyes.
abstract: 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 application potential of 3-DAC and 4-DAC in two-photon polymerization (TPP) was studied. Both dyes could be used directly as initiators in TPP. The TPP threshold energies of the corresponding resins were as low as the best reported results. High-resolution 2D and 3D nanopatterns containing low amounts of small molecule residue were successfully fabricated by TPP, demonstrating the extensive application prospects of these dyes in the fabrication of micromachines, microsensor arrays and biomedical devices.
authors.affiliation: Technical Institute of Physics and Chemistry, CAS, Beijing 100190, PR China.
authors.forename: Jianqiang
authors.initials: J
authors.lastname: Xue
authors.forename: Yuxia
authors.initials: Y
authors.lastname: Zhao
authors.forename: Feipeng
authors.initials: F
authors.lastname: Wu
authors.forename: De-Cai
authors.initials: DC
authors.lastname: Fang