T. Itaya et al., CHARGE-TRANSFER COMPLEXATION IN AQUEOUS POLYELECTROLYTE SOLUTION .2. INTERACTION BETWEEN POLYCATIONS AND CT COMPLEXES, Bulletin of the Chemical Society of Japan, 67(8), 1994, pp. 2047-2052
The CT complexation between 9,10-dimethoxyanthracene-2-sulfonate ion (
DMACS-; donor) and 9,10-anthraquinone-2-sulfonate ion (AQS-; acceptor)
has been studied in aqueous solution of poly(1,1-dimethyl-3,5-dimethy
lenepiperidinium chloride) (PDDP+Cl-). In aqueous PDDP+Cl- solution, b
oth DMACS- and AQS- are electrostatically bound to the polyion and the
CT complex between them is formed around the polyion due to the close
proximity of DMACS(-)-AQS- pairs. By comparing the CT complexation in
aqueous PDDP+Cl- solution with that in aqueous poly(allylammonium chl
oride) (PAAH+Cl-) solution studied previously, the effects of the char
ge density of the polyion, the structure of charged groups on the poly
ion and the local conformation of the polyion upon the CT complexation
have been clarified. A plausible structure of the CT complex has been
determined so as to satisfy the symmetry-allowed interaction between
the HOMO of DMACS- and the LUMO of AQS-. The CT complex interacts more
strongly with the polyion than Cl- and the decrease in the viscosity
of the polymer (the contraction of the polymer chain) is more effectiv
ely caused by the CT complexation. Moreover, the strength of the assoc
iation (stacking interaction) of aromatic counterions (DMACS-, AQS-) i
ncluding the CT complexation affects the binding of these counterions
to the polyion.