Azo-dimethylaminopyridine functionalized Ni(II)-Porphyrin as a Photoswitchable Nucleophilic Catalyst

  1. Jannis Ludwig,
  2. Julian Helberg,
  3. Hendrik ZipseORCID Logo and
  4. Rainer HergesORCID Logo

Submitting author affiliation: Universität Kiel, Kiel, Germany

Beilstein Arch. 2020, 202070. doi:10.3762/bxiv.2020.70.v1

Published 09 Jun 2020

  • Preprint

Abstract

We present the synthesis and the photochemical and catalytic switching properties of an azopyridine as a photoswitchable ligand, covalently attached to a Ni(II)-porphyrin. Upon irradiation with 530 nm (green light), the azopyridine switches to the cis configuration and coordinates with the Ni2+ ion. Light of 435 nm (violet) isomerizes the ligand back to the trans configuration, which decoordinates for steric reasons. This so-called record player design has been used previously to switch the spin state of Ni2+ between singlet and triplet. We now use the coordination/decoordination process to switch the catalytic activity of the dimethylaminopyridine (DMAP) unit. DMAP is a known catalyst in the nitroaldol (Henry) reaction. Upon coordination to the Ni2+ ion, the basicity of the pyridine lone pair is attenuated and hence the catalytic activity is reduced. Decoordination restores the catalytic activity. The rate constants in the two switching states differ by a factor of 2.2, and the catalytic switching is reversible.

Keywords: Ni(II) porphyrins; photoswitch; record player molecules; nitroaldol reaction; nucleophilic catalyst; catalysis

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When a peer-reviewed version of this preprint is available in the Beilstein Journals, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information:

Ludwig, J.; Helberg, J.; Zipse, H.; Herges, R. Beilstein Arch. 2020, 202070. doi:10.3762/bxiv.2020.70.v1

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