Limitations and design considerations for donor-acceptor systems in luminescent solar concentrators: The effect of coupling-induced red-edge absorption

Luminescent solar concentrators (LSCs) use luminescence and waveguiding to concentrate photons within thin dielectric slabs for use in photovoltaic, lighting, and photobioreactor applications. Donor-acceptor systems of organic chromophores are widely used in LSCs to broaden the sunlight absorption range and attempt to reduce loss-inducing reabsorption by the emitting chromophore. We use raytrace simulations across a large parameter space to model the performance of LSCs containing two novel donor-acceptor trimers based on the perylene moiety. We find that under certain conditions, trimers outperform single-dye LSCs as expected. However, at higher concentrations, a slight increase in red-edge absorption by the trimers increases reabsorption and has a deleterious effect on LSC performance. This underscores the large effect that even small changes in the red edge can have, and may discourage the use of donor-acceptor schemes with high interchromophore coupling that promotes red-edge absorption. Finally, we show that for a LSC-PV pair, selecting a PV cell that is well-matched with the LSC emission spectrum has a large effect on the flux gain of the system, and that the systems studied here are well-matched to emerging PV technologies

Quantifying highly efficient incoherent energy transfer in perylene-based multichromophore arrays

Multichromophore perylene arrays were designed and synthesized to have extremely efficient resonance energy transfer. Using broadband ultrafast photoluminescence and transient absorption spectroscopies, transfer timescales of approximately 1 picosecond were resolved, corresponding to efficiencies of up to 99.98%. The broadband measurements also revealed spectra corresponding to incoherent transfer between localized states. Polarization resolved spectroscopy was used to measure the dipolar angles between donor and acceptor chromophores, thereby enabling geometric factors to be fixed when assessing the validity of Förster theory in this regime. Förster theory was found to predict the correct magnitude of transfer rates, with measured ∼2-fold deviations consistent with the breakdown of the point-dipole approximation at close approach. The materials presented, along with the novel methods for quantifying ultrahigh energy transfer efficiencies, will be valuable for applications demanding extremely efficient energy transfer, including fluorescent solar concentrators, optical gain, and photonic logic devices

Competing Energy Transfer Pathways in a Five-Chromophore Perylene Array

A perylene (donor–dimer)–acceptor–(donor–dimer) pentamer array is synthesized to investigate the competition between excimer formation and Förster resonance energy transfer. Using time-resolved fluorescence, we show that, upon excitation, the isolated perylene dimer forms an excimer with a time constant of 4.3 ns. However, in the pentamer array, when either of two constituent dimers donate their energy to the acceptor fluorophore, the excimer energy trap is eliminated. The pentamer macromolecule shows broad absorption and reduced self-absorption, at some cost to fluorescence quantum yield

Thermodynamic Factors Impacting the Peptide-Driven Self-Assembly of Perylene Diimide Nanofibers

Synthetic peptides offer enormous potential to encode the assembly of molecular electronic components, provided that the complex range of interactions is distilled into simple design rules. Here, we report a spectroscopic investigation of aggregation in an extensive series of peptide-perylene diiimide conjugates designed to interrogate the effect of structural variations. By fitting different contributions to temperature dependent optical absorption spectra, we quantify both the thermodynamics and the nature of aggregation for peptides by incrementally varying hydrophobicity, charge density, length, as well as asymmetric substitution with a hexyl chain, and stereocenter inversion. We find that coarse effects like hydrophobicity and hexyl substitution have the greatest impact on aggregation thermodynamics, which are separated into enthalpic and entropic contributions. Moreover, significant peptide packing effects are resolved via stereocenter inversion studies, particularly when examining the nature of aggregates formed and the coupling between π electronic orbitals. Our results develop a quantitative framework for establishing structure–function relationships that will underpin the design of self-assembling peptide electronic materials