A series of nine soluble, symmetric chalcogenophenes bearing hexyl-substituted triphenylamines, indolocarbazoles, or phenylcarbazoles was designed and synthesized as potential two-photon absorption (2PA) initiators. A detailed photophysical analysis of these molecules revealed good 2PA properties of the series and, in particular, a strong influence of selenium on the 2PA cross sections, rendering these materials especially promising new 2PA photoinitiators. Structuring and threshold tests proved the efficiency and broad spectral versatility of two selenium-containing lead compounds as well as their applicability in an acrylate resin formulation. A comparison with commercial photoinitiators Irg369 and BAPO as well as sensitizer ITX showed that the newly designed selenium-based materials TPA-S and TPA-BBS outperform these traditional initiators by far both in terms of reactivity and dose. Moreover, by increasing the ultralow concentration of TPA-BBS, a further reduction of the polymerization threshold can be achieved, revealing the great potential of this series for application in two-photon polymerization (2PP) systems where only low laser power is available.

In this work we present the design, synthesis and systematic investigation of the optical properties of symmetric triphenylamine (TPA)-substituted thiophenes. The use of electron-donating (-OMe, -tBu, -Me, -TMS), -neutral (-H) or -withdrawing (-F, -CN, -SO₂Me) substituents gives rise to D-A-D based two-photon absorption (2PA) chromophores. The photophysical properties of these compounds, including one-photon absorption and 2PA using two-photon-excited fluorescence, were investigated in different organic solvents with varying polarity. The maximum 2PA cross sections prove to be strongly dependent on the nature of the TPA substituent and range between  ca. 173 GM (Goeppert-Mayer units) and 379 GM. Although most of the investigated substances also exhibit high fluorescence quantum yields, two-photon absorption screening tests of an acrylate monomer formulation revealed the efficiency of these materials as 2PA photoinitiators. These results are supported by quantum chemical calculations of the spin density distribution indicating that the mechanism of polymerization initiation using acrylate monomer is favored by strong localization of the unpaired electrons in the triplet state on the C2 carbon of the thiophene moiety.

Two-photon induced polymerization (2PP) based 3D printing is a powerful microfabrication tool. Specialized two-photon initiators (2PIs) are critical components of the employed photosensitive polymerizable formulations. This work investigates the cooperative enhancement of two-photon absorption cross sections (σ_2PA) in a series of 1,3,5-triazine-derivatives bearing 1-3 aminostyryl-donor arms, creating dipolar, quadrupolar and octupolar push-pull systems. The multipolar 2PIs were successfully prepared and characterized, σ_2PA were determined using z-scan at 800 nm as well as spectrally resolved two-photon excited fluorescence measurements, and the results were compared to high-level ab initio computations. Modern tunable femtosecond lasers allow 2PP-processing at optimum wavelengths tailored to the absorption behavior of the 2PI. 2PP structuring tests revealed that while performance at 800 nm is similar, at their respective σ_2PA-maxima the octupolar triazine-derivative outperforms a well-established ketone-based quadrupolar reference 2PI, with significantly lower fabrication threshold at exceedingly high writing speeds up to 200 mm/s and a broader window for ideal processing parameters.

The possibility of the direct encapsulation of living cells via two-photon induced photopolymerization enables the microfabrication of hydrogel scaffolds with high initial cell loadings and intimate matrix-cell contact. While highly efficient water-soluble two-photon initiators based on benzylidene ketone dyes have been developed, they exhibit considerable cyto- and phototoxicity. To address the problem of photoinitiator migration from the extracellular matrix into the cytosol, a two-photon initiator bound to a polymeric hyaluronan backbone (HAPI) was synthesized in this work. HAPI exhibited a distinct improvement of cytocompatibility compared to a reference two-photon initiator. Basic photophysical investigations were performed to characterize the absorption and fluorescence behavior of HAPI. Laser scanning microscopy was used to visualize and confirm the hindered transmembrane migration behavior of HAPI. The performance of HAPI was tested in two-photon polymerization at exceedingly high printing speeds of 100 mm s-1 producing gelatin-based complex 3D hydrogel scaffolds with a water content of 85%. The photodamage of the structuring process was low and viable MC3T3 cells embedded in the gel were monitored for several days after structuring.