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Issue 11, 2018
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Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids

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Enriched semiconducting single-walled carbon nanotubes (SWCNT (6,5) and SWCNT (7,6)) and HiPco nanotubes were covalently functionalized with either zinc phthalocyanine or silicon phthalocyanine as electron donors. The synthetic strategy resulted in edge-on and face-on geometries with respect to the phthalocyanine geometry, with both phthalocyanines held by an electronically conducting diphenylacetylene linker. The extent of functionalization in the MPc-SWCNT (M = Zn or Si) donor–acceptor nanohybrids was determined by systematic studies involving AFM, TGA, XPS, optical and Raman techniques. Intramolecular interactions in MPc-SWCNT nanohybrids were probed by studies involving optical absorbance, Raman, luminescence and electrochemical studies. Different degrees of interactions were observed depending on the type of MPc and mode of attachment. Substantial quenching of MPc fluorescence in these hybrids was observed from steady-state and three-dimensional fluorescence mapping, which suggests the occurrence of excited state events. Evidence for the occurrence of excited state charge transfer type interactions was subsequently secured from femtosecond transient absorption studies covering both the visible and near-infrared regions. Furthermore, electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor revealed accumulation of one-electron reduced product upon continuous irradiation of the nanohybrids. In such experiments, the ZnPc-SWCNT (6,5) nanohybrid outperformed other nanohybrids and this suggests that this is a superior donor–acceptor system for photocatalytic applications.

Graphical abstract: Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids

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Supplementary files

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The article was received on 10 Jan 2018, accepted on 16 Feb 2018 and first published on 16 Feb 2018

Article type: Paper
DOI: 10.1039/C8NR00262B
Citation: Nanoscale, 2018,10, 5205-5213

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    Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids

    L. M. Arellano, L. Martín-Gomis, H. B. Gobeze, D. Molina, C. Hermosa, M. J. Gómez-Escalonilla, J. L. G. Fierro, Á. Sastre-Santos, F. D'Souza and F. Langa, Nanoscale, 2018, 10, 5205
    DOI: 10.1039/C8NR00262B

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