Sensitive efficiency of photoinduced electron transfer to band gaps of semiconductive single-walled carbon nanotubes with supramolecularly attached zinc porphyrin bearing pyrene glues

Eranda Maligaspe, Atula S D Sandanayaka, Taku Hasobe, Osamu Ito, Francis Dsouza

Research output: Contribution to journalArticle

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Abstract

Photoinduced electron transfer in self-assembled single-walled carbon nanotube (SWNT)/zinc porphyrin (ZnP) hybrids utilizing (7,6)- and (6,5)-enriched SWNTs has been investigated. Toward this, first, zinc porphyrin was covalently functionalized to possess four pyrene entities (ZnP(pyr)4). Exfoliation of the semiconducting nanotube bundles occurred due to π-π-type interactions with the pyrene and porphyrin entities in organic solvents. The nanohybrids thus formed were isolated and characterized by TEM, UV-visible-near-IR, and Raman spectroscopy. Free-energy calculations suggested the possibility of electron transfer in both the (7,6)- and (6,5)-possessing ZnP(pyr)4/SWNT nanohybrids. Accordingly, fluorescence studies revealed efficient quenching of the singlet excited state of ZnP in the nanohybrids, originating from the charge separation, as confirmed by observation of a ZnP π-cation radical in transient absorption spectra. The rates of charge separation were found to be slightly higher for (7,6)-SWNT-derived hybrids compared to the (6,5)-SWNT-derived hybrids. Charge recombination revealed an opposite effect, indicating that the (7,6)-SWNTs are slightly better for charge stabilization compared to the (6,5)-SWNTs. The present nanohybrids were further utilized to photochemically reduce the hexyl viologen dication in the presence of a sacrificial electron donor in an electron-pooling experiment, offering additional proof for the occurrence of photoinduced charge separation and potential utilization of these materials in light-energy-harvesting applications. Finally, solar cells constructed using the ZnP/SWNT hybrids revealed higher efficiency for the ZnP(pyr)4/(7,6)-SWNT hybrid with narrower nanotube band gap compared with the ZnP(pyr)4/(6,5)-SWNT having a relatively wider band gap.

Original languageEnglish
Pages (from-to)8158-8164
Number of pages7
JournalJournal of the American Chemical Society
Volume132
Issue number23
DOIs
Publication statusPublished - 2010 Jun 16

Fingerprint

Bearings (structural)
Carbon Nanotubes
Glues
Pyrene
Porphyrins
Single-walled carbon nanotubes (SWCN)
Adhesives
Energy gap
Zinc
Electrons
Nanotubes
Viologens
pyrene
zinc hematoporphyrin
Raman Spectrum Analysis
Energy harvesting
Excited states
Organic solvents
Genetic Recombination
Free energy

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Sensitive efficiency of photoinduced electron transfer to band gaps of semiconductive single-walled carbon nanotubes with supramolecularly attached zinc porphyrin bearing pyrene glues. / Maligaspe, Eranda; Sandanayaka, Atula S D; Hasobe, Taku; Ito, Osamu; Dsouza, Francis.

In: Journal of the American Chemical Society, Vol. 132, No. 23, 16.06.2010, p. 8158-8164.

Research output: Contribution to journalArticle

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