A photolabile ruthenium‐based complex, [Ru(bpy)2(4AMP)2](PF6)2, (4AMP=4‐(aminomethyl)pyridine) is incorporated into polyurea organo‐ and hydrogels via the reactive amine moieties on the photocleavable 4AMP ligands. While showing long‐term stability in the dark, cleavage of the pyridine–ruthenium bond upon irradiation with visible or near‐infrared irradiation (in a two‐photon process) leads to rapid de‐gelation of the supramolecular gels, thus enabling spatiotemporal micropatterning by photomasking or pulsed NIR‐laser irradiation

Polymers that, upon photochemical activation with visible light, undergo rapid degradation to small molecules are described. Through functionalization of a polyphosphazene backbone with pendant coumarin groups sensitive to light, polymers which are stable in the dark could be prepared. Upon irradiation, cleavage of the coumarin moieties exposes carboxylic acid moieties along the polymer backbone. The subsequent macromolecular photoacid is found to catalyze the rapid hydrolytic degradation of the polyphosphazene backbone. Water-soluble and non-water-soluble polymers are reported, which due to their sensitivity toward light in the visible region could be significant as photocleavable materials in biological applications.

A simple supramolecular crosslinked gel is reported with a photosensitive ruthenium bipyridine complex functioning as a crosslinker and poly(4‐vinylpyridine) (P4VP) as a macromolecular ligand. Irradiation of the organogels in H2O/MeOH with visible and NIR light (in a multiphoton process) leads to cleavage of pyridine moieties from the ruthenium complex breaking the cross‐links and causing degelation and hence solubilization of the P4VP chains. Real‐time (RT) photorheology experiments of thin films showed a rapid degelation in several seconds, whereas larger bulk samples could also be photocleaved. Furthermore, the gels could be reformed or healed by simple heating of the system and restoration of the metal–ligand crosslinks. The relatively simple dynamic system with a high sensitivity towards light in the visible and NIR region make them interesting positive photoresists for nano/micropatterning applications, as was demonstrated by writing, erasing, and rewriting of the gels by single‐ and multiphoton lithography.

Der lichtempfindliche Rutheniumkomplex [Ru-(bpy) 2 (4AMP) 2 ](PF 6 ) 2 (4AMP = 4-(Aminomethyl)pyridin) wurde über die reaktiven Aminogruppen der durchL icht abspaltbaren 4AMP-Liganden in Polyharnstoff-Organo-oder -Hydrogele eingebaut. Im Dunkeln sind diese Gele sehr stabil. DurchB estrahlen mit sichtbarem Lichto der NIR-Strahlung (letzteres mittels Zweiphotonenabsorption) werden die Ruthenium-Pyridin-Bindungen gespalten, was zum Abbau des supramolekularen Gels führt. Dies ermçglicht eine räumlich und zeitlicha ufgelçste Mikrostrukturierung des Gels mithilfe einer Photomaske oder eines gepulsten NIR-Lasers.