Upgrading the Toolbox: Two-Photon Absorption Induced Cleavage of Coumarin Dimers for Light-Based 4D Printing.

The use of light for shaping and changing matter is of high relevance in polymer and material science. Herein, a photopolymer method is presented, which comprises the combination of 3D photo-printing at 405 nm light and subsequent modification under two-photon absorption (TPA) conditions at 532 nm light, adding the fourth dimension. The TPA-triggered cycloreversion reaction of an intramolecular coumarin dimer (ICD) structure occurs within the absorbing material.

Cycloreversion performance of coumarin and hetero-coumarin dimers under aerobic conditions: unexpected behavior triggered by UV-A light.

Photochemical [2+2]-cycloadditions of coumarin-like monomers are the textbook paradigms of photo-formation and photo-cleavage reactions. The electronic conjugation length of monomers and dimers is quite different which results in almost fully separated UV/Vis absorption bands in the UV-A and UV-C. This feature enables the selective light-controlled conversion between monomeric and dimeric forms by the choice of the appropriate wavelengths.