Iodine doping of substituted μ-carbido iron diphthalocyanines

Abstract

Hemi and amphi-substituted µ-carbido iron diphthalocyanine having general formula (t-bu) 4 PcFe-C-FePc and (t-bu) 4 PcFe-C-FePc(t-bu) 4 have been oxidized with I 2 . The oxidized compounds have been characterized and their physicochemical properties have been studied; the results obtained lead to assign them the formula [(t-Bu) 4 PcFe-C-FePc] (I 5 ) 0.66 and [[(t-Bu) 4 PcFe] 2 C]] (I 5 ) 0.66 respectively. The conduction properties, related to the role played by the pushing groups inserted in the peripheral macrocycles, are discussed. Moreover, an effective purification method for improving the yield and purity of iron tetra-tert-butyl phthalocyanine is described, the difficulty being able to obtain this precursor with a high purity grade.

Iodine‐Doped Cobalt Phthalocyanine Supported on Multiwalled Carbon Nanotubes for Electrocatalysis of Oxygen Reduction Reaction

“…The spectrum of the iodine doped CoPyPc also shows broadening. The broadening of the Q band was attributed to the presence of a radical species 14. The presence of a radical was clearly proved in this work using EPR, Figure 3.…”

“…The red shift of the Q‐band in the spectra on iodine doping of phthalocyanine has been reported 14 suggesting the narrowing of the highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gap. The spectrum of the iodine doped CoPyPc also shows broadening.…”

“…The presence of iodine doped CoPyPc on the SEM of MWCNT is observed by the increase in white spots. Phthalocyanines are known to exhibit metallic behavior when partially oxidized and adopting a face‐to‐face stacking 13,14; hence the iodised CoPyPc‐MWCNT nanocomposite shows more reflective surface features on SEM images. TEM images of the MWCNT, Figure 5B(i), clearly show the MWCNT bundles, which show increased black spots and a granulated structure (as highlighted on the image) following mixing with iodine doped CoPyPc, Figure 5B(ii).…”

“…Doped nanocomposites appear to be one way that can be used to improve on ORR electrocatalysis 5–12. Some metallophthalocyanine derivatives were found to have improved conductivity upon iodine‐doping 13,14. Apart from one study 15 using iodine doped unsubstituted cobalt phthalocyanine (CoPc), oxygen reduction using iodine doped phthalocyanines has not been explored.…”

Comparative electrocatalytic studies of nanocomposites of mixed and covalently linked multiwalled carbon nanotubes and 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II)

“…The mixed nanocomposite for CoPyPc showed a red-shift of 6 nm in comparison to CoPyPc alone. The red shift of the Q-band in the spectra of nanocomposites gives evidence to the reduction of highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) energy gap [31], caused by the presence of MWCNT. The destabilization/reduction of the HOMO-LUMO energy gap is an intrinsic property of a material necessary for use in electrocatalysis.…”