We report the synthesis, self-assembly, and electron transfer capabilities of peptide-based electron donor-acceptor molecules and supramolecular nanostructures. These modified peptides contain π-conjugated oligothiophene electron donor cores that are peripherally substituted with naphthalene diimide electron acceptors installed via imidation of site-specific lysine residues. These molecules self-assemble into one-dimensional nanostructures in aqueous media, as shown through steady-state absorption, photoluminescence, and circular dichroism spectra, as well as transmission electron microscopy. Excitation of the oligothiophene donor moieties results in electron transfer to the acceptor units, ultimately creating polar, charge-separated states that persist for over a nanosecond as observed with transient absorption spectroscopy. This study demonstrates how transient electric fields can be engineered into aqueous nanomaterials of biomedical relevance through external, temporally controlled photonic inputs.

There is substantial urgency to create artificial light-harvesting systems that are relatively inexpensive and capable of absorbing a significant fraction of the solar spectrum. Molecular materials possess a number of attractive characteristics for this purpose, such as their light weight, spectral tunability, and the potential to use self-assembly to form large structures capable of executing multiple photophysical processes required for photoelectric energy conversion. In this work, we demonstrate that ionically assembled complexes composed of oppositely charged conjugated polyelectrolytes (CPEs) that function as excitonic donor/acceptor pairs possess 10 significant potential as artificial energy transfer antennae. We find that, upon complexation in water, excitation energy is transferred from the donor to the acceptor CPE in less than 250 fsa timescale that is competitive with natural light-harvesting antennae. We further find that the state of CPE chain extension and thus spatial delocalization of the excited-state wavefunction can be readily manipulated using the relative polyion charge ratio, allowing us to tune the emission quantum yield of the CPE in a straight-forward manner. Collectively, our results point toward the fact that the extension of a CPE chain upon complexation is a cooperative phenomenon between multiple chains even at dilute polymer concentrations.

The ultrafast formation of bound charge pairs, or polaron pairs (PPs), in mixed-order aggregates of poly(3-hexylthiophene) was investigated using femtosecond stimulated Raman spectroscopy (FSRS). Spectral dynamics in the carbon-carbon stretching region reveal a significant photoinduced depletion in steady-state features associated with lamellar-stacked, ordered polymer regions upon 500 nm photoexcitation; this is followed by the appearance of red-shifted features attributable to PPs that is delayed by a few hundred femtoseconds. PP features decay with concomitant recovery of the steady-state Raman depletion over a few picoseconds. The vibrational spectrum of the PP obtained exhibits a modest red shift (<15 cm(-1)) and lower Raman activity relative to steady-state features in the C═C stretching region but similar features in other regions. In total, this work demonstrates the potential of time-resolved Raman as a morphologically selective and structurally sensitive probe for tracking ultrafast charge separation and recombination dynamics within polymer regions of conjugated materials.

Mobilities and lifetimes of photogenerated charge carriers are core properties of photovoltaic materials and can both be characterized by contactless terahertz or microwave measurements. Here, the expertise from fifteen laboratories is combined to quantitatively model the current‐voltage characteristics of a solar cell from such measurements. To this end, the impact of measurement conditions, alternate interpretations, and experimental inter‐laboratory variations are discussed using a (Cs,FA,MA)Pb(I,Br)3 halide perovskite thin‐film as a case study. At 1 sun equivalent excitation, neither transport nor recombination is significantly affected by exciton formation or trapping. Terahertz, microwave, and photoluminescence transients for the neat material yield consistent effective lifetimes implying a resistance‐free JV‐curve with a potential power conversion efficiency of 24.6 %. For grainsizes above ≈20 nm, intra‐grain charge transport is characterized by terahertz sum mobilities of ≈32 cm2 V−1 s−1. Drift‐diffusion simulations indicate that these intra‐grain mobilities can slightly reduce the fill factor of perovskite solar cells to 0.82, in accordance with the best‐realized devices in the literature. Beyond perovskites, this work can guide a highly predictive characterization of any emerging semiconductor for photovoltaic or photoelectrochemical energy conversion. A best practice for the interpretation of terahertz and microwave measurements on photovoltaic materials is presented.

An important challenge in the study of conjugated organic materials is to relate the properties of transient states underlying macroscopic material responses directly with intra- and intermolecular structure. We discuss recent efforts using the vibrational sensitivity of time-resolved Raman spectroscopy to interrogate structural properties of transient excited and charge-separated states in conjugated oligomers and polymers in order to relate them to molecular conformations and material microstructures. We focus on recent work with excited-state Raman spectroscopy that provides mode-specific signatures of structural relaxation in oligo- and polythiophenes, examination of structural heterogeneities associated with exciton localization in different structural motifs of amorphous polymers, and interrogation of correlations between microstructure and properties and dynamics of charge-separated states within polymer aggregates. On the basis of these recent efforts, we provide an outlook for further applying this method to elucidate relationships between the structure and properties of transient states and the photoresponses of conjugated materials.