1,7,9,10-Tetrasubstituted PMIs Accessible through Decarboxylative Bromination: Synthesis, Characterization, Photophysical Studies, and Hydrogen Evolution Catalysis

Daniel Costabel; Artem Skabeev; Afshin Nabiyan; Yusen Luo; Johannes B Max; Ashwene Rajagopal; Daniel Kowalczyk; Benjamin Dietzek; Maria Wächtler; Helmar Görls; Dirk Ziegenbalg; Yulian Zagranyarski; Carsten Streb; Felix H Schacher; Kalina Peneva

doi:10.1002/chem.202004326

1,7,9,10-Tetrasubstituted PMIs Accessible through Decarboxylative Bromination: Synthesis, Characterization, Photophysical Studies, and Hydrogen Evolution Catalysis

Chemistry. 2021 Feb 24;27(12):4081-4088. doi: 10.1002/chem.202004326. Epub 2021 Jan 25.

Authors

Daniel Costabel¹, Artem Skabeev¹, Afshin Nabiyan¹, Yusen Luo², Johannes B Max¹, Ashwene Rajagopal³, Daniel Kowalczyk⁴, Benjamin Dietzek^{2

5

6}, Maria Wächtler^{2

5}, Helmar Görls⁷, Dirk Ziegenbalg⁴, Yulian Zagranyarski⁸, Carsten Streb³, Felix H Schacher^{1

6}, Kalina Peneva^{1

6}

Affiliations

¹ Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Lessingstraße 8, 07743, Jena, Germany.
² Institute of Physical Chemistry, Abbe Center of Photonics, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.
³ Institute of Inorganic Chemistry 1, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
⁴ Institute of Chemical Engineering, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
⁵ Department of Functional Interfaces, Leibniz Institute of Photonic Technology Jena, Albert-Einstein-Straße 9, 07745, Jena, Germany.
⁶ Center for Energy and Environmental Chemistry Jena and, Jena Center of Soft Matter, Friedrich Schiller University Jena, Philosophenweg 7a, 07743, Jena, Germany.
⁷ Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldt Straße 8, 07743, Jena, Germany.
⁸ Faculty of Chemistry and Pharmacy, Sofia University "St. Kliment Ohridski", 1 James Bourchier Blvd., 1164, Sofia, Bulgaria.

Abstract

In this work, we present a new synthetic strategy for fourfold-substituted perylene monoimides via tetrabrominated perylene monoanhydrides. X-ray diffraction analysis unveiled the intramolecular stacking orientation between the substituents and semicircular packing behavior. We observed the remarkable influence of the substituent on the longevity and nature of the excited state upon visible light excitation. In the presence of poly(dehydroalanine)-graft-poly(ethylene glycol) graft copolymers as solubilizing template, the chromophores are capable of sensitizing [Mo₃ S₁₃ ]^2- clusters in aqueous solution for stable visible light driven hydrogen evolution over three days.

Keywords: hydrogen evolution; organic dyes; perylene monoimides; photosensitizers; transient absorption.

Grants and funding

SFB 234/ 364549901/Deutsche Forschungsgemeinschaft