Premium
Core Perylene Diimide Designs via Direct Bay‐ and ortho ‐(Poly)trifluoromethylation: Synthesis, Isolation, X‐ray Structures, Optical and Electronic Properties
Author(s) -
Clikeman Tyler T.,
Bukovsky Eric V.,
Wang XueBin,
Chen YuSheng,
Rumbles Garry,
Strauss Steven H.,
Boltalina Olga V.
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201501024
Subject(s) - perylene , diimide , chemistry , imide , electrochemistry , solvent , photochemistry , crystallography , polymer chemistry , molecule , organic chemistry , electrode
We developed an efficient solvent‐ and catalyst‐free direct polytrifluoromethylation of solid perylene‐3,4,9,10‐tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay‐ and ortho ‐substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady‐state and time‐resolved emission, X‐ray diffraction, electrochemical, and gas‐phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho , and imide positions in the new PDIs. Solid‐state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Analysis of the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects from substituting electron‐withdrawing groups at all three positions.