Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces

Boyang Mao, David González Calatayud, Vincenzo Mirabello, Navaratnarajah Kuganathan, Haobo Ge, Robert M. J. Jacobs, Ashley M. Shepherd, José Alberto Ribeiro Martins, Jorge Bernardino De La Serna, Benjamin J Hodges, Stanley W. Botchway, Sofia Ioana Pascu

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Abstract

Two new routes to functionalized SWNTs have been established using a bulky Zn(II)-porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this Zinc(II)-substituted, bulky aryl porphyrin and those of the corresponding new nano-composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: (i) the supramolecular interactions between the pristine SWNTs and Zn(II)-porphyrin by virtue of π-π stacking, and (ii) a novel covalent binding strategy based on the Bingel reaction. We investigated the nature of the porphyrin aggregates forming on flat surfaces by Steady-state and time-resolved fluorescence emission spectroscopies and imaging techniques including fluorescence lifetime imaging microscopy (FLIM) together with Atomic Force Microscopy (AFM) and Super Resolution Stimulated Emission Depletion microscopy (STED). X-ray photoelectron spectroscopy (XPS) studies highlighted the differences in the covalent versus non-covalent attachments of functional metalloporphyrins to SWNTs. Gas phase density functional theory (DFT) calculations (implemented in CASTEP) indicated that the Zinc(II) porphyrin interacts non-covalently with SWNT to form a donor-acceptor complex. The appendage of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalization of the SWNTs surface.
Original languageEnglish
Pages (from-to)9772-9789
JournalChemistry - A European Journal
Volume23
Issue number41
Early online date25 Apr 2017
DOIs
Publication statusPublished - 21 Jul 2017

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    Mao, B., Calatayud, D. G., Mirabello, V., Kuganathan, N., Ge, H., Jacobs, R. M. J., Shepherd, A. M., Ribeiro Martins, J. A., Bernardino De La Serna, J., Hodges, B. J., Botchway, S. W., & Pascu, S. I. (2017). Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces. Chemistry - A European Journal, 23(41), 9772-9789. https://doi.org/10.1002/chem.201605232