Morphology-Dependent Energy Transfer Dynamics in Fluorene-Based Amphiphile Nanoparticles

Nanoparticles are interesting systems to study because of their large range of potential uses in biological imaging and sensing. We investigated molecular nanoparticles formed by fast injection of a small volume of molecularly dissolved fluorene-derivative amphiphilic molecules into a polar solvent, which resulted in solid spherical particles of ∼80 nm diameter with high stability. Energy transfer studies were carried out on two-component nanoparticles that contained mixtures of donor and acceptor amphiphiles of various fractions. We conducted time-resolved photoluminescence measurements on the two-component nanoparticles in order to determine whether the fundamental donor-acceptor interaction parameter (the Förster radius) depends on the acceptor concentration. The Förster radius was found to be large for very low incorporated acceptor fractions (<0.1%), but it declined with increasing concentration. These changes were concomitant with shifts in the acceptor emission and absorption circular dichroism spectra that indicated an increasing clustering of acceptors into domains as their fraction was raised. In addition, for acceptor fractions below 2% the extracted Förster radii were found to be significantly larger than predicted from donor-acceptor spectral overlap calculations, in accordance with efficient excitation diffusion within the donor matrix, aiding the overall transfer to acceptors. We conclude that energy transfer in two-component nanoparticles shows a complex interplay between phase segregation of the constituent donor and acceptor molecules and excitation diffusion within their domains.