Wavelength-Gated Photochemical Synthesis of Phenalene Diimides

Florian Feist; Sarah L Walden; Jessica Alves; Susanna V Kunz; Aaron S Micallef; Aidan J Brock; John C McMurtrie; Tanja Weil; James P Blinco; Christopher Barner-Kowollik

doi:10.1002/anie.202016632

Wavelength-Gated Photochemical Synthesis of Phenalene Diimides

Angew Chem Int Ed Engl. 2021 Apr 26;60(18):10402-10408. doi: 10.1002/anie.202016632. Epub 2021 Mar 18.

Authors

Florian Feist^{1

2

3

4

5}, Sarah L Walden^{1

2}, Jessica Alves^{1

2}, Susanna V Kunz^{1

2}, Aaron S Micallef¹, Aidan J Brock^{1

2}, John C McMurtrie^{1

2}, Tanja Weil³, James P Blinco^{1

2}, Christopher Barner-Kowollik^{1

2

4

5}

Affiliations

¹ Centre for Materials Science, Queensland University of Technology (QUT), 2 George St., Brisbane, QLD, 4000, Australia.
² School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George St., Brisbane, QLD, 4000, Australia.
³ Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, 55128, Mainz, Germany.
⁴ Macromolecular Architectures, Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131, Karlsruhe, Germany.
⁵ Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.

Abstract

Herein, we pioneer a wavelength-gated synthesis route to phenalene diimides. Consecutive Diels-Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro-phenalene-1,6-diol diimides via 5-formyl-hexahydro-benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82-99 % yield) and exhibit excellent diastereoselectivity (62-98 % d.r.). The wavelength-gated nature of the stepwise reaction enables the modular construction of phenalene diimide scaffolds by choice of substrate and wavelength. Importantly, this synthetic methodology opens a facile avenue to a new class of persistent phenalenyl diimide neutral radicals, constituting a versatile route to spin-active molecules.

Keywords: Diels-Alder reaction; ortho-quinodimethane; persistent neutral radicals; phenalene diimide; wavelength-gated synthesis.

Abstract

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