Surface Modifications: Interactions between an Aryl Thioacetate‐Functionalized Zn(II) Porphyrin and Graphene Oxide (Adv. Funct. Mater. 5/2016)

Abstract

Design and synthesis of a novel porphyrin‐based nanohybrid, whereby the entire surface of GO is modified via supramolecular assembly, is reported by S. I. Pascu and co‐workers on page 687. The Zn(II)‐porphyrin@GO nanohybrid forms stable dispersions in ethanol, likely containing free and bound Zn(II)‐porphyrin in a dynamic exchange. New opportunities for using uniform dispersions of tailor‐made nanohybrids incorporating GO within layered materials are opened up.

Fluorescence‐Lifetime Imaging and Super‐Resolution Microscopies Shed Light on the Directed‐ and Self‐Assembly of Functional Porphyrins onto Carbon Nanotubes and Flat Surfaces

“…It has already been shown that Zn‐porphyrins can be functionalised and their self‐assembly can generate nanorings of 5–60 porphyrin units . Earlier observations by AFM or STM measurements performed on drop‐casted solutions show that such supramolecular architectures can be described as nanocrystalline aggregates of porphyrins, having a shape of a ring or tower, with sizes varying in the range of hundreds of nanometers, depending on the imaging method used to evaluate the size …”

“…We characterised these materials in a thin film environment using fluorescence lifetime measurements via time‐correlated single photon counting (TCSPC) combined with multi‐photon laser scanning confocal microscopy; this allows us to gain detailed information on the environment of the fluorophore upon immobilisation within the nanomaterial hybrid and estimate the influence of the different linking strategies on the emerging materials′ optical properties by observing their quenching characteristics in solution and in the solid state …”

“…The intrinsic sp 2 nature of the CÀCb ond of the SWNT allows reaction with organic molecules bearing specific functional groupst hat react with the outer walls of the tubular material. Porphyrins have been used as versatile chromophores, having the ability to act as dispersing agentsf or carbon nanomaterials and to decorateC 60 , [5] carbon nanotubes, [6] graphene oxide [7] or nanohorns [8] in artificial photosynthetic devices. [9] SWNTsc an interact via aromatic stacking with electron-rich planar molecules resultingi ns upramolecular donor-acceptor complexes.S uch molecules, including porphyrins (planar,e lectron-rich, aromatic species), are characterisedbyremarkably high extinction coefficients in the visible region.…”

“…We characterised these materials in at hin film environment using fluorescence lifetimem easurements via time-correlated single photon counting (TCSPC) combined with multi-photon laser scanning confocal microscopy;t his allows us to gain detailed information on the environment of the fluorophore upon immobilisation within the nanomaterial hybrid and estimate the influence of the different linking strategies on the emerging materials' opticalp roperties by observing their quenching characteristics in solutiona nd in the solid state. [7,12] Characterisation approaches rely on severald ifferente fficient and novel physical measurement methods coupled with multi-scalem icroscopies to identify unequivocally the existence of ac ovalent and non-covalentl inkage between small organic molecules and carbon nanomaterials. The approach reported herein can become ag eneral methodology for achieving controlo fp hotochemistry and sensing capabilities of aw ide range of opticala nd energy materials by tailoringt he nature of the interactions between components using directed-and self-assembly processes in solutionand thin film.…”

“…The recent work by Strano and collaborators has demonstrated the potential of non‐covalent sensors based on SWNTs in biology . Thiol‐derivatised functional Zn II porphyrin‐based systems have not been investigated thus far in the context of generating new SWNTs adducts with targeted optical properties. The combination of the unique electron transport properties of the SWNTs together with the promising photochemical properties of tailor‐made functional porphyrins could render their new adducts as potential candidates for dispersible solid state scaffolds in nano‐optoelectronic devices and bio‐sensing.…”