Charge stabilizing tris(triphenylamine)-zinc porphyrin–carbon nanotube hybrids: synthesis, characterization and excited state charge transfer studies

Abstract

Functionalization of single-walled (SWCNTs) and double-walled carbon nanotubes (DWCNTs) with a charge stabilizing zinc porphyrin functionalized with triphenylamine entities has been accomplished. The synthetic approach involved the reaction of tris-(triphenylamine)porphyrinato zinc(II) with iodobenzene functionalized nanotubes through a Sonogashira C–C cross coupling reaction under microwave irradiation conditions. Evidence of covalent functionalization and the extent of functionalization was obtained from systematic studies carried out by AFM, TGA, XPS and Raman spectroscopy techniques. The porphyrin–nanotube interactions in the SWCNT–porphyrin hybrid were probed by studies involving optical absorbance, Raman spectroscopy, steady-state and time resolved emission and electrochemical studies. The fluorescence of porphyrin in this hybrid was found to be quenched due to interactions with the CNTs. Femtosecond transient absorption spectral studies covering both the visible and near-infrared regions were supportive of excited state charge transfer interactions in the zinc porphyrin–SWCNT. The charge separated state was persistent for about 1 ns. Electron pooling experiments suggested that this donor–acceptor nanohybrid could be a useful photocatalyst.