A Convenient Synthesis of Pentaporphyrins and Supramolecular Complexes with a Fulleropyrrolidine

Abstract

A simple and straightforward synthesis of diporphyrins and pentaporphyrins is reported here. The supramolecular interactions of the new porphyrin derivatives with C60 and PyC60 (a pyridyl [60]fulleropyrrolidine) were evaluated by absorption and fluorescence titrations in toluene. While no measurable modifications of the absorption and fluorescence spectra were observed upon addition of C60 to the porphyrin derivatives, the addition of PyC60 to the corresponding mono-Zn(II) porphyrins resulted in the formation of Zn(porphyrin)–PyC60 coordination complexes and the binding constants were calculated. Results show that the four free-base porphyrin units in pentaporphyrin 6 have a significant contribution in the stabilization of the 6–PyC60 complex. The crystal and molecular features of the pentaporphyrin Zn5 were unveiled using single-crystal X-ray diffraction studies.

New Route to Glycosylated Porphyrins via Aromatic Nucleophilic Substitution (SNAr)—Synthesis and Cellular Uptake Studies

“…Similarly to carbohydrate chemistry, the S N Ar functionalisation of porphyrins has been widely exploited at particular positions, namely, the meso - or β -position [ 16 ]. Peripheral meso -phenyl ring functionalisation has been reported [ 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ], mostly on perfluorinated derivatives, while for nitroporphyrins S N Ar has been suggested as a side-reactivity only [ 26 , 27 ]. Hence, it is a promising challenge for both group of compounds—sugars and porphyrins—to functionalise and combine them via the unexplored side.…”

Tetrapyrrolic Macrocycles: Synthesis, Functionalization and Applications 2018

“…Considering that porphyrins and fullerenes are attractive building blocks in the design of supramolecular assemblies, Tomé and co-workers report a selective and efficient synthetic access to diporphyrins and pentaporphyrins through the reaction of 5-(4-hydroxyphenyl)-10,15,20-tri phenylporphyrin with 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin or with its Zn(II) complex [1]. The authors verified that the four free-base porphyrin units present in the pentaporphyrin coordinated with Zn (II) have an important contribution in the stabilization of the complex obtained during titrations with a pyridyl[60]fulleropyrrolidine derivative presumably due to a synergic effect between the fullerene unit and the four free-base porphyrin units mediated by π-π interactions.…”