Aggregation-Enhanced Two-Photon Absorption of Anionic Conjugated Polyelectrolytes.

The two-photon absorption properties of anionic poly(phenylene ethynylene)-type conjugated oligo- and polyelectrolytes are studied in molecularly dissolved and aggregated forms in aqueous solution. Several different polyvalent cations are used to induce aggregation. It is found that both materials in the aggregated form exhibit enhanced two-photon excited fluorescence (2PEF) and two-photon cross section (σ) compared with the molecularly dissolved structures. The 2PEF and σ are unaffected by the nature of the polyvalent cation that is used to induce aggregation. The two-photon absorption cross section enhancement arises because of the increase in the difference dipole moment (Δμ) in the aggregates of the conjugated materials, an effect that is attributed to the introduction of charge transfer character into the aggregate excited state.