Broad Spectral Domain Fluorescence Wavelength Modulation of Visible and Near-Infrared Emissive Polymersomes

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Abstract
Incorporation of an extended family of multi[(porphinato)zinc(II)] (PZn)-based supermolecular fluorophores into the lamellar membranes of polymersomes (50 nm to 50 mum diameter polymer vesicles) gives rise to electrooptically diverse nano-to-micron (meso) scale soft materials. Studies that examine homogeneous suspensions of 100 nm diameter emissive polymersomes demonstrate fluorescence energy modulation over a broad spectral domain of the visible and near-infrared (600-900 nm). These polymersomal structures highlight that the nature of intermembranous polymer-to-fluorophore contacts depends on the position and identity of the porphyrins' phenyl ring substituents. Emissive polymersomes are shown to possess reduced spectral heterogeneity with respect to the established optical signatures of these PZn-based supermolecular fluorophores in solution; additionally, selection of fluorophore ancillary substituents predictably controls the nature of polymer-emitter noncovalent interactions to provide an important additional mechanism to further modulate the fluorescence band maxima of these meso-scale emissive vesicles.