Selective Bromination of Perylene Diimides under Mild Conditions
- 30 June 2007
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 72 (16) , 5973-5979
Abstract
A novel method for the bromination of perylene diimides, PDI (1), under mild conditions is reported. Variation of the reaction conditions allows mono- and dibromination of PDIs to afford 2 and 3 (these can be separated through standard procedures) or exclusive dibromination to afford 3. Pure 1,7 regioisomers are obtained through repetitive crystallization. The structure of 1,7-3b was elucidated by a single-crystal X-ray analysis. The facility of the bromination reaction, which decreases in the order 1a > 1b > 1c, depends on PDI aggregation propensities. Monobrominated PDIs were utilized for the syntheses of novel unsymmetrical piperidinyl (4a and 4b) and trimethylsilylethynyl derivatives (5a and 5b). Computational studies (DFT) on imide substituent rotation in PDIs reveal that in the case of bulky groups there is a restricted rotation leading to isomers, in agreement with our experimental results. An aromatic core twist in PDIs bearing one and two bromine substituents was also investigated by DFT.Keywords
This publication has 20 references indexed in Scilit:
- Organic Thin Film Transistors Based on Cyclohexyl-Substituted Organic SemiconductorsChemistry of Materials, 2005
- A Novel Fluorescent Dye with Strong, Anisotropic Solid‐State Fluorescence, Small Stokes Shift, and High PhotostabilityAngewandte Chemie International Edition, 2005
- Synthesis of a Bis(pyridyl)-Substituted Perylene Diimide Ligand and Incorporation into a Supramolecular Rhomboid and Rectangle via Coordination Driven Self-AssemblyThe Journal of Organic Chemistry, 2004
- An Iridium Difluoroketene Complex: Synthesis and IsolationAngewandte Chemie International Edition, 2004
- Preparation and Characterization of Regioisomerically Pure 1,7-Disubstituted Perylene Bisimide DyesThe Journal of Organic Chemistry, 2004
- Combining Light-Harvesting and Charge Separation in a Self-Assembled Artificial Photosynthetic System Based on Perylenediimide ChromophoresJournal of the American Chemical Society, 2004
- Synthesis and Excited-State Photodynamics of Perylene−Porphyrin Dyads. 1. Parallel Energy and Charge Transfer via a Diphenylethyne LinkerThe Journal of Physical Chemistry B, 2001
- Liquid Crystalline Perylene Diimides: Architecture and Charge Carrier MobilitiesJournal of the American Chemical Society, 2000
- Using redundant internal coordinates to optimize equilibrium geometries and transition statesJournal of Computational Chemistry, 1996
- Optimization of equilibrium geometries and transition structuresJournal of Computational Chemistry, 1982