Driving Force Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes.

We investigate the thermodynamic driving-force dependences of photoinduced charge separation (CS) and subsequent charge transfer dynamics in single-walled carbon nanotube (SWNT)-perylenediimide (PDI) donor-acceptor (D-A) superstructures. Pump-probe spectroscopy reveals that [SWNT(•+)n]-(PDI-•)n CS states form on an ∼100 fs time scale following photoexcitation; these dynamics are invariant across an ∼400 mV driving force range, indicating that SWNT hole polaron formation time scales are determined by nanotube lattice and solvent relaxation. These CS states feature SWNT hole polarons adjacent to (geminate) and nearby (nongeminate) PDI radical anions. Analysis of the free energy dependence for charge recombination (CR) of [SWNT•+]geminate-(PDI-•) CS states highlights an ∼2 meV value for D-A electronic coupling (HAB) and ∼0.93 eV for the total reorganization energy (λT). A corresponding driving force dependence of the CR dynamics for [SWNT•+]nongeminate-(PDI-•) CS states indicates a diminished HAB value (∼0.6 meV) and a larger λT (∼1.1 eV), consistent with larger transfer distances. SWNT excitons that persist following photoinduced CS drive photooxidation of PDI-• components of [SWNT(•+)n]-(PDI-•)n CS states (1SWNT* + PDI•- → PDI + SWNT•-); this reaction manifests a significantly reduced λT value (∼0.67 eV) as the initially prepared SWNT reduced state bears the character of a conduction band injected electron ([SWNT•-]CB). This reaction thus gives rise to relaxed, nongeminate SWNT electron and hole polarons on the same nanotube; these polarons react on a 102 ps time scale independent of the electronic structure of these SWNT-PDI superstructures.

• Publication year

  2025

• Venue

  Journal of the American Chemical Society

• Publication date

  2025-11-11

• Fields of study

  Materials Science, Physics, Medicine

• Identifiers
  DOI 10.1021/jacs.5c14868PMID 41217974
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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