Light triggers molecular shuttling in rotaxanes: control over proximity and charge recombination

Maximilian Wolf (1) , Ayumu Ogawa (2, 3) , Mareike Bechtold (1, 4) , Maxime Vonesch (3) , Jennifer Wytko (3) , Koji Oohora (2) , Stéphane Campidelli (5) , Takashi Hayashi (2) , Dirk Guldi (1) , Jean Weiss (3)

1 ICMM - Inorganic Chemistry, Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM)
2 Division of Applied Chemistry, Graduate School of Engineering, Osaka University
3 Institut de Chimie de Strasbourg
4 KIT - Karlsruhe Institute of Technology
5 LICSEN - Laboratoire Innovation en Chimie des Surfaces et NanoSciences

We present the synthesis of novel rotaxanes based on mechanically interlocked porphyrins and fullerene and their advanced investigations by means of photophysical measurements. To this end, a fullerene-capped dumbbell-type axle containing a central triazole was threaded through strapped (metallo)porphyrins—either a free-base or a zinc porphyrin. Femtosecond-resolved transient absorption measurements revealed charge-separation between the porphyrin and fullerene upon light excitation. Solvent polarity and solvent coordination effects induced molecular motion of the rotaxanes upon charge separation and enabled, for the first time, subtle control over the charge recombination by enabling and controlling the directionality of shuttling.

Domains: Coordination chemistry; Chemical Physics [physics.chem-ph]; Optics [physics.optics]

Maximilian Wolf, Ayumu Ogawa, Mareike Bechtold, Maxime Vonesch, Jennifer Wytko, et al.. Light triggers molecular shuttling in rotaxanes: control over proximity and charge recombination. Chemical Science, 2019, 10 (13), pp.3846-3853. ⟨10.1039/C8SC05328F⟩. ⟨cea-02068179⟩