Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly

Jean-Hubert Olivier, Jaehong Park, Pravas Deria, Jeff Rawson, Yusong Bai, Amar S. Kumbhar, Michael J. Therien

Research output: Contribution to journalArticle

10 Scopus citations

Abstract

Single-walled carbon nanotube (SWNT)-based nanohybrid compositions based on (6,5) chirality-enriched SWNTs ([(6,5) SWNTs]) and a chiral n-type polymer (S-PBN(b)-Ph4PDI) that exploits a perylenediimide (PDI)-containing repeat unit are reported; S-PBN(b)-Ph4PDI-[(6,5) SWNT] superstructures feature a PDI electron acceptor unit positioned at 3 nm intervals along the nanotube surface, thus controlling rigorously SWNT-electron acceptor stoichiometry and organization. Potentiometric studies and redox-titration experiments determine driving forces for photoinduced charge separation (CS) and thermal charge recombination (CR) reactions, as well as spectroscopic signatures of SWNT hole polaron and PDI radical anion (PDI-.) states. Time-resolved pump-probe spectroscopic studies demonstrate that S-PBN(b)-Ph4PDI-[(6,5) SWNT] electronic excitation generates PDI-. via a photoinduced CS reaction (τCS≈0.4 ps, ΦCS≈0.97). These experiments highlight the concomitant rise and decay of transient absorption spectroscopic signatures characteristic of the SWNT hole polaron and PDI-. states. Multiwavelength global analysis of these data provide two charge-recombination time constants (τCR≈31.8 and 250 ps) that likely reflect CR dynamics involving both an intimately associated SWNT hole polaron and PDI-. charge-separated state, and a related charge-separated state involving PDI-. and a hole polaron site produced via hole migration along the SWNT backbone that occurs over this timescale.

Original languageEnglish (US)
Pages (from-to)8133-8138
Number of pages6
JournalAngewandte Chemie - International Edition
Volume54
Issue number28
DOIs
StatePublished - Jul 1 2015
Externally publishedYes

Keywords

  • nanoscale assembly
  • photoinduced charge-transfer
  • redox-active polymers
  • semiconducting materials
  • single-walled nanotubes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Fingerprint Dive into the research topics of 'Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly'. Together they form a unique fingerprint.

  • Cite this