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Durham University

Department of Chemistry

Publication details for Dr Lars-Olof Pålsson

Monkman, A. P., Pålsson, L.-O., Higgins, R. W. T., Wang, C. S., Bryce, M. R., Batsanov, A. S. & Howard, J. A. K. (2002). Protonation and subsequent intramolecular hydrogen bonding as a method to control chain structure and tune luminescence in heteroatomic conjugated polymers. Journal Of The American Chemical Society 124(21): 6049-6055.

Author(s) from Durham


We report the effects of protonation on the structural and spectroscopic properties of
1,4-dimethoxy-2,5-bis(2-pyridyl)benzene (9) and the related AB coploymer poly{2,5-pyridylene-co-1,4-[2,5-
bis(2-ethylhexyloxy)]phenylene} (7). X-ray crystallographic analysis of 9, 1,4-dimethoxy-2,5-bis(2-pyridyl)-
benzene bis(formic acid) complex 10, and 1,4-dimethoxy-2,5-bis(2-pyridinium)benzene bis(tetrafluoroborate
salt) (11) establishes that reaction of formic acid with 9 does not form an ionic pyridinium salt in the solid
state, rather, the product 10 is a molecular complex with strong hydrogen bonds between each nitrogen
atom and the hydroxyl hydrogen in formic acid. In contrast, reaction of 9 with tetrafluoroboric acid leads to
the dication salt 11 with significant intramolecular hydrogen bonding (N-HâââO-Me) causing planarization
of the molecule. The pyridinium and benzene rings in 11 form a dihedral angle of only 3.9° (cf. pyridinebenzene
dihedral angles of 35.4° and 31.4° in 9, and 43.8° in 10). Accordingly, there are large red shifts
in the optical absorption and emission spectra of 11, compared to 9 and 10. Polymer 7 displays a similar
red shift in its absorption and photoluminescence spectra upon treatment with strong acids in neutral solution
(e.g. methanesulfonic acid, camphorsulfonic acid, and hydrochloric acid). This is also observed in films of
polymer 7 doped with strong acids. Excitation profiles show that emission arises from both protonated and
nonprotonated sites in the polymer backbone. The protonation of the pyridine rings in polymer 7,
accompanied by intramolecular hydrogen bonding to the oxygen of the adjacent solubilizing alkoxy
substituent, provides a novel mechanism for driving the polymer into a near-planar conformation, thereby
extending the ð-conjugation, and tuning the absorption and emission profiles. The electroluminescence of
a device of configuration ITO/PEDOT/polymer 7/Ca/Al is similarly red-shifted by protonation of the polymer.