Exploring the Synthesis and Properties of Fluorinated Cationic Triangulenes and Their Precursors
Ramandeep Kaur1, Jules Moutet1, David D Mills1
1Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, 85750, United States.
Abstract:
Fluorination of tris(2,6-dimethoxyphenyl)-methylium ((DMP)3C+) was achieved through the partial defluorination of the methyl 2,3,5,6-tetrafluorobenzoate via nucleophilic aromatic substitution. Using the fluorinated 2F((DMP)3C+) as a precursor, fluorinated tetramethoxy- and dimethoxyquin- acridinium salts (2F4 and 2F5 respectively) and trioxo-, azadioxo-, and diazaoxo- triangulenium salts (2F6, 2F7 and 2F8 respectively) were synthesized successfully in good to moderate yields. Fluorination induced significant red shifts in absorption (16 to 29 nm) and emission (13 to 41 nm) maxima, and increased electrophilicity as evidenced by lower reduction potentials. X-ray structural analysis showed distinct packing patterns compared to the non-fluorinated analogues, indicating the presence of molecular dipoles.
Related Concept Videos
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group...
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Thermal and Photochemical Electrocyclic Reactions: Overview
Cationic Chain-Growth Polymerization: Mechanism
VSEPR Theory and the Effect of Lone Pairs
Radicals: Electronic Structure and Geometry
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...


