TY - JOUR
T1 - Fluorescence Lifetime Imaging and Super resolution microscopies shed light on the directed- and self-assembly of functional porphyrins onto carbon nanotubes and flat surfaces
AU - Mao, Boyang
AU - Calatayud, David González
AU - Mirabello, Vincenzo
AU - Kuganathan, Navaratnarajah
AU - Ge, Haobo
AU - Jacobs, Robert M. J.
AU - Shepherd, Ashley M.
AU - Ribeiro Martins, José Alberto
AU - Bernardino De La Serna, Jorge
AU - Hodges, Benjamin J
AU - Botchway, Stanley W.
AU - Pascu, Sofia Ioana
PY - 2017/7/21
Y1 - 2017/7/21
N2 - 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.
AB - 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.
UR - https://doi.org/10.1002/chem.201605232
U2 - 10.1002/chem.201605232
DO - 10.1002/chem.201605232
M3 - Article
VL - 23
SP - 9772
EP - 9789
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 41
ER -