Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties

David Schmidt; Minjung Son; Jong Min Lim; Mei-Jin Lin; Ivo Krummenacher; Holger Braunschweig; Dongho Kim; Frank Würthner

doi:10.1002/anie.201507039

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties

Angew Chem Int Ed Engl. 2015 Nov 16;54(47):13980-4. doi: 10.1002/anie.201507039. Epub 2015 Sep 9.

Authors

David Schmidt¹, Minjung Son², Jong Min Lim², Mei-Jin Lin¹, Ivo Krummenacher³, Holger Braunschweig³, Dongho Kim⁴, Frank Würthner⁵

Affiliations

¹ Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany).
² Yonsei University, Spectroscopy Laboratory for Functional π-Electronic Systems, and Department of Chemistry, Seoul 120-749 (Korea).
³ Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074 Würzburg (Germany).
⁴ Yonsei University, Spectroscopy Laboratory for Functional π-Electronic Systems, and Department of Chemistry, Seoul 120-749 (Korea). dongho@yonsei.ac.kr.
⁵ Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany). wuerthner@chemie.uni-wuerzburg.de.

PMID: 26350026
DOI: 10.1002/anie.201507039

Abstract

Unprecedented neutral perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4-hydroxyaryl-substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open-shell singlet biradical ground state for the PBI biradical OS-2(..) (〈s(2)〉=1.2191) with a relatively small singlet-triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72.

Keywords: biradicals; dyes; perylene bisimides; pigments; radicals.

Publication types

Research Support, Non-U.S. Gov't