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Title: Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-Ray Structures, Optical and Electronic Properties

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. Moreover, 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.
 [1] ;  [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [1]
  1. Colorado State Univ., Fort Collins, CO (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Univ. of Chicago, IL (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1434-193X
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: European Journal of Organic Chemistry; Journal Volume: 2015; Journal Issue: 30; Related Information: European Journal of Organic Chemistry
ChemPubSoc Europe
Research Org:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
14 SOLAR ENERGY; 77 NANOSCIENCE AND NANOTECHNOLOGY Aromatic substitution; Electrochemistry; Liquid chromatography; ­ Fluorescence; Dyes/pigments; Fluorine