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Enhancement of the Two-Photon Initiating Efficiency of a Thioxanthone Derivative through a Chevron-Shaped Architecture

  作者 MALVAL JEANPIERRE; JIN MING; MORLETSAVARY FABRICE; CHAUMEIL HELENE; DEFOIN ALBERT; SOPPERA OLIVIER; SCHEUL TEODORA; BOURIAU MICHEL; BALDECK PATRICE L  
  选自 期刊  Chemistry of Materials;  卷期  2011年23-15;  页码  3411-3420  
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[摘要]We investigated the one- and two-photon excitation properties of a new hybrid anthracene thioxanthone (ANTX) system, which was assembled into a chevron-shaped molecular architecture. Such a geometrical association first preserves the high efficiency of the free radical photoinitiator and leads, in the same time, to a strong increase in the two-photon absorption (2PA) cross section by more than a factor of 30 as compared to thioxanthone (TX). A four-state model was required to fit the 2PA spectrum of ANTX, which clearly undergoes a strong enhancement in the low-frequency region. As a consequence, ANTX constitutes a suitable two-photon initiating chromophore with a much higher efficiency as TX used as reference. At lambda(exc) = 710 nm for instance, we showed that the two-photon polymerization threshold of ANTX is five times lower with respect to that of TX. Additionally, we demonstrated by the fabrication of three-dimensional microstructures that this new hybrid system remains two-photon activable when excited at wavelengths near its one-photon absorption region as suggested by the sum overstates model. We also show that this new two-photon initiator exhibits a higher reactivity than a diaminofluorene derivative, which is commonly used in two-photon polymerization.

 
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