Formed through cooperative self-assembly of amphiphilic diblock copolymers and electronically conjugated porphyrinic near-infrared (NIR) fluorophores (NIRFs), NIR-emissive polymersomes (50 nm to 50 μm diameter polymer vesicles) define a family of organic-based, soft-matter structures that are ideally suited for deep-tissue optical imaging and sensitive diagnostic applications. Here, we describe magic angle and polarized pump–probe spectroscopic experiments that: (i) probe polymersome structure and NIRF organization and (ii) connect emitter structural properties and NIRF loading with vesicle emissive output at the nanoscale. Within polymersome membrane environments, long polymer chains constrain ethyne-bridged oligo(porphinato)zinc(II) based supermolecular fluorophore (>PZnn) conformeric populations and disperse these >PZnn species within the hydrophobic bilayer. Ultrafast excited-state transient absorption and anisotropy dynamical studies of NIR-emissive polymersomes, in which the >PZnn fluorophore loading per nanoscale vesicle is varied between 0.1–10 mol %, enable the exploration of concentration-dependent mechanisms for nonradiative excited-state decay. These experiments correlate fluorophore structure with its gross spatial arrangement within specific nanodomains of these nanoparticles and reveal how compartmentalization of fluorophores within reduced effective dispersion volumes impacts bulk photophysical properties. As these factors play key roles in determining the energy transfer dynamics between dispersed fluorophores, this work underscores that strategies that modulate fluorophore and polymer structure to optimize dispersion volume in bilayered nanoscale vesicular environments will further enhance the emissive properties of these sensitive nanoscale probes.
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