Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties.
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.
Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany).
David
D
Schmidt
Yonsei University, Spectroscopy Laboratory for Functional π-Electronic Systems, and Department of Chemistry, Seoul 120-749 (Korea).
Minjung
M
Son
Yonsei University, Spectroscopy Laboratory for Functional π-Electronic Systems, and Department of Chemistry, Seoul 120-749 (Korea).
Jong Min
JM
Lim
Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany).
Mei-Jin
MJ
Lin
Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074 Würzburg (Germany).
Ivo
I
Krummenacher
Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074 Würzburg (Germany).
Holger
H
Braunschweig
Yonsei University, Spectroscopy Laboratory for Functional π-Electronic Systems, and Department of Chemistry, Seoul 120-749 (Korea). dongho@yonsei.ac.kr.
Dongho
D
Kim
Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany). wuerthner@chemie.uni-wuerzburg.de.
Frank
F
Würthner
biradicals; dyes; perylene bisimides; pigments; radicals