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

8 Citations (Scopus)

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

Fingerprint

Semiconducting polymers
Carbon Nanotubes
Single-walled carbon nanotubes (SWCN)
Charge carriers
Carbon nanotubes
Gene Conversion
perylenediimide
Electrons
Chirality
Titration
Stoichiometry
Nanotubes
Anions
Polymers
Negative ions
Experiments
Pumps

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly. / Olivier, Jean-Hubert; Park, Jaehong; Deria, Pravas; Rawson, Jeff; Bai, Yusong; Kumbhar, Amar S.; Therien, Michael J.

In: Angewandte Chemie - International Edition, Vol. 54, No. 28, 01.07.2015, p. 8133-8138.

Research output: Contribution to journalArticle

Olivier, Jean-Hubert ; Park, Jaehong ; Deria, Pravas ; Rawson, Jeff ; Bai, Yusong ; Kumbhar, Amar S. ; Therien, Michael J. / Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly. In: Angewandte Chemie - International Edition. 2015 ; Vol. 54, No. 28. pp. 8133-8138.
@article{1262054a408c4cfaa21efb69c4bc21bd,
title = "Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly",
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.",
keywords = "nanoscale assembly, photoinduced charge-transfer, redox-active polymers, semiconducting materials, single-walled nanotubes",
author = "Jean-Hubert Olivier and Jaehong Park and Pravas Deria and Jeff Rawson and Yusong Bai and Kumbhar, {Amar S.} and Therien, {Michael J.}",
year = "2015",
month = "7",
day = "1",
doi = "10.1002/anie.201501364",
language = "English (US)",
volume = "54",
pages = "8133--8138",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "28",

}

TY - JOUR

T1 - Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer-Wrapped Carbon Nanotube Assembly

AU - Olivier, Jean-Hubert

AU - Park, Jaehong

AU - Deria, Pravas

AU - Rawson, Jeff

AU - Bai, Yusong

AU - Kumbhar, Amar S.

AU - Therien, Michael J.

PY - 2015/7/1

Y1 - 2015/7/1

N2 - 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.

AB - 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.

KW - nanoscale assembly

KW - photoinduced charge-transfer

KW - redox-active polymers

KW - semiconducting materials

KW - single-walled nanotubes

UR - http://www.scopus.com/inward/record.url?scp=85027918454&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027918454&partnerID=8YFLogxK

U2 - 10.1002/anie.201501364

DO - 10.1002/anie.201501364

M3 - Article

AN - SCOPUS:85027918454

VL - 54

SP - 8133

EP - 8138

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 28

ER -