Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with light and acid-base equilibria, have emerged as highly attractive molecular units. The challenge in their design comes from the need to accommodate application-defined boundary conditions for both light- and protonation-responsivity. Here we combine time-resolved spectroscopic studies, on time scales ranging from femtoseconds to seconds, with density functional theory (DFT) calculations to elucidate and apply the acidochromism of a recently designed iminothioindoxyl (ITI) photoswitch. We show that protonation of the thermally stable Z isomer leads to a strong batochromically-shifted absorption band, allowing for fast isomerization to the metastable E isomer with light in the 500-600 nm region. Theoretical studies of the reaction mechanism reveal the crucial role of the acid-base equilibrium which controls the populations of the protonated and neutral forms of the E isomer. Since the former is thermally stable, while the latter re-isomerizes on a millisecond time scale, we are able to modulate the half-life of ITIs over three orders of magnitude by shifting this equilibrium. Finally, stable bidirectional switching of protonated ITI with green and red light is demonstrated with a half-life in the range of tens of seconds. Altogether, we designed a new type of multi-responsive molecular switch in which protonation red-shifts the activation wavelength by over 100 nm and enables efficient tuning of the half-life in the millisecond-second range.

Centre for Systems Chemistry Stratingh Institute for Chemistry Faculty of Science and Engineering University of Groningen Nijenborgh 7 9747 AG Groningen The Netherlands

Department of Chemistry Faculty of Natural Sciences Matej Bel University Tajovského 40 SK 97400 Banská Bystrica Slovak Republic

European Laboratory for Non Linear Spectroscopy via N Carrara 1 50019 Sesto Fiorentino Italy

ICCOM CNR via Madonna del Piano 10 50019 Sesto Fiorentino Italy

Laboratoire CEISAM UMR UN CNRS 6230 Université de Nantes Nantes F 44000 France

Radboud University Institute for Molecules and Materials FELIX Laboratory Toernooiveld 7c 6525 ED Nijmegen The Netherlands

Regional Centre of Advanced Technologies and Materials Faculty of Science Palacký University in Olomouc Šlechtitelů 27 CZ 771 46 Olomouc Czech Republic

University Medical Center Groningen Department of Radiology Medical Imaging Center University of Groningen Hanzeplein 1 9713 GZ Groningen The Netherlands

Van't Hoff Institute for Molecular Sciences University of Amsterdam Science Park 904 1098 XH Amsterdam The Netherlands

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Getting a molecular grip on the half-lives of iminothioindoxyl photoswitches