Influence of Anion Variations on Morphological, Spectral, and Physical Properties of the Propidium Luminophore.

Abstract

Propidium iodide (3,8-diamino-5-[3-(diethylmethylammonio)propyl]-6-phenylphenanthridinium diiodide, [P][I]), is a well-known red fluorescent dye that is widely used for biological applications such as staining. In this study, we have replaced the iodide counteranion of [P][I] with three hydrophobic and bulky organic anions, trifluoromethanesulfonate/[TfO], bis(trifluoromethanesulfonyl)imide/[NTf2], and bis(perfluoroethylsulfonyl)imide/[BETI], and have thus obtained a propidium-derived group of uniform materials based on organic salts (PGUMBOS). The morphological, spectral, and physical properties of these materials were investigated in order to understand the impact of anion variations. While [P][I] is a crystalline solid, propidium salts with [BETI] or [NTf2] counteranions, i.e., [P][BETI] and [P][NTf2], have significantly lower crystallinity as reflected in powder X-ray diffraction data. In addition, [P][BETI] and [P][NTf2] exhibited improved photothermal stability as compared to [P][I] when examined using thermogravimetric analysis and time-dependent kinetic fluorescence experiments under the given experimental conditions. Spectral and electronic properties of the propidium luminophore were not significantly changed upon anion variations, although fluorescence lifetimes and quantum yields showed a systematic increase with decreasing solvent polarity. The experimental HOMO-LUMO energy gaps of these compounds were ∼2 eV with energies of HOMO and LUMO orbitals obtained as -5.15 (±0.08) and -3.19 (±0.08) eV.