title: Water-Soluble Spiropyrans with Inverse Photochromism and Their Photoresponsive Electrostatic Self-Assembly.
abstract: A new type of light responsive nanoscale assemblies based on water-soluble spiropyrans is presented. We have synthesized four anionic spiropyrans bearing multiple sulfonate groups and investigated their photochromic behavior in aqueous solution. Depending on the pH, either inverse photochromism (acidic conditions) or normal photochromism (alkaline conditions) is found. Kinetic data for the interconversion of the spiropyran and merocyanine isomers including the subsequent slow hydrolysis have been obtained by UV/Vis spectroscopy. The results show that the spiropyrans undergo hydrolysis in both alkaline and acidic solution, while in the latter the rate is far slower than in the former. This prolonged hydrolytic stability together with the inverse photochromism under acidic conditions makes the sulfonated spiropyrans suitable to build photoresponsive nanostructures with cationic polyelectrolytes. We show how the self-assembly process is driven by electrostatic interactions and how the spiropyrans' photochromic property allows the size control of the supramolecular objects by visible light. The assembly size is characterized by dynamic light scattering and TEM. In addition, UV/Vis and fluorescence spectroscopy and ζ-potential measurements help to explain the size change upon visible light irradiation.
authors.affiliation: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058, Erlangen, Germany.
authors.forename: Daniel
authors.identifier: http://orcid.org/0000-0002-8673-0068
authors.initials: D
authors.lastname: Moldenhauer
authors.affiliation: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058, Erlangen, Germany.
authors.forename: Franziska
authors.identifier: http://orcid.org/0000-0003-1016-2583
authors.initials: F
authors.lastname: Gröhn
keywords: photochromism; photoresponsive; polyelectrolytes; self-assembly; spiropyrans