Structural characterization of quinoxaline homopolymers and quinoxaline/ether sulfone copolymers by matrix-assisted laser desorption ionization mass spectrometry.
Polyphenylquinoxalines (PPQs) are prepared from self-polymerizable quinoxaline monomers that carry fluorine, hydroxyaryl (ArOH), and phenyl substituents. In basic media, these monomers self-polymerize via a series of nucleophilic aromatic substitution reactions (SNAr), in which aromatic enolates (ArO- nucleophiles) attack the electrophilic carbons bearing F leaving groups to effect fluoride displacement. Polyphenylquinoxaline/polyether-sulfone (PPQ/PES) copolymers are synthesized similarly by combining self-polymerizable quinoxaline monomers with a 1:1 molar mixture of 4,4'-dichlorodiphenyl sulfone and bisphenol A. The MALDI mass spectra of the polymers reveal that the major products up to approximately 15,000 Da molecular mass are homo- or copolymeric macrocycles. Linear byproducts are also observed, arising from nucleophilic ring opening of already formed macrocycles. Oligomers containing at least one PPQ unit readily protonate upon MALDI, whereas PES homopolymers require alkali metal ion addition to become detectable. Molecular orbital calculations point out that the nucleophilic and electrophilic reactivities of the PPQ monomer and the PPQ growing chains generated during propagation are comparable, allowing for continued condensations via SN-Ar, until cyclization terminates this process. The calculations also predict a significantly lower electrophilic reactivity for carbons substituted by chlorine instead of fluorine, justifying the discrimination against incorporation of PES units observed for the copolymers. The computationally optimized structures of PPQ and PPQ/PES macrocycles show a diverse array of cavity sizes and geometries which depend on the size of the macrocycle, the sequence of the repeat units, and the position of the substituents in the quinoxaline ring; quinoxaline pendants (phenyl groups) are found to favor helical arrangements in the prepared macrocycles.
Polce
M J
MJ
Department of Chemistry, The University of Akron, Ohio 44325, USA.
Klein
D J
DJ
Harris
F W
FW
Modarelli
D A
DA
Wesdemiotis
C
C