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Localization/Delocalization of Charges in Bay‐Linked Perylene Bisimides
Author(s) -
Jiang Wei,
Xiao Chengyi,
Hao Linxiao,
Wang Zhaohui,
Ceymann Harald,
Lambert Christoph,
Di Motta Simone,
Negri Fabrizia
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103954
Subject(s) - perylene , delocalized electron , chemistry , exciton , photochemistry , absorption spectroscopy , vibronic coupling , copper , valence (chemistry) , conjugated system , crystallography , stereochemistry , computational chemistry , molecule , physics , organic chemistry , quantum mechanics , polymer
The copper‐mediated Ullmann coupling of 1,7‐dibromoperylene bisimides afforded structurally perfect singly‐linked perylene bisimide (PBI) arrays, whilst the homo‐coupling of 1,12‐dibromoperylene bisimides gave doubly‐linked and triply‐linked diperylene bisimides. The interactions of three bay‐linked diperylene bisimides that differed in their linkage (singly, doubly, and triply) were investigated in their neutral and reduced forms (mono‐anion to tetra‐anion). UV/Vis absorption and fluorescence spectroscopy revealed different degrees of interaction, which was explained by exciton coupling and conjugation effects. The electrochemical properties and spectroelectrochemistry also showed quite‐different degrees of PBI interactions in the reduced mixed‐valence species, which was apparent by the observation of CT bands. The interpretation of the experimental findings was supported by spin‐restricted and ‐unrestricted DFT and time‐dependent TD‐DFT calculations with the long‐range‐corrected CAM‐B3LYP functional. Accordingly, the degree of interaction in both the neutral and reduced forms of the bay‐linked PBIs was qualitatively in the order doubly linked