5,10,15,20-tetrakis(pentafluorophenyl)porphyrin reacts with a range of nucleophiles (amines, alcohols, thiols, nitrogen heterocycles, and others) resulting in the nucleophilic aromatic substitution of the para-F atoms of the pentafluorophenyl groups. This reaction, which was fortuitously discovered by Kadish and collaborators in 1990, is now being extensively used to synthesize porphyrins bearing electron-donating substituents in the para-position of their meso-aryl groups. This mini-review highlights the methods of synthesis of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, the use of its metal complexes in catalysis and its reaction with nucleophiles to yield new monomeric porphyrins, porphyrins supported in polymers or new polymeric porphyrin matrices useful for heterogeneous catalysis.

Abstract:In recent years, several synthetic strategies aiming at the peripheral functionalization of porphyrins were developed. Particularly interesting are those involving the modification of β-pyrrolic positions leading to pyrrole-modified porphyrins containing four-, five-, six-or seven-membered heterocycles. Azeteoporphyrins, porpholactones and morpholinoporphyrins are representative examples of such porphyrinoids. These porphyrin derivatives have recently gained an increasing interest due to their potential application in PDT, as multimodal imaging contrast agents, NIR-absorbing dyes, optical sensors for oxygen, cyanide, hypochlorite and pH, and in catalysis.

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Here, we present a novel conjugate based on a weakly electron-donating Zn(II)-meso-tetrakis(pentafluorophenyl)porphyrin linked to a strongly electron-accepting C 60 . From spectroscopic and electrochemical investigations a 1.9 eV high charge-separated state is derived. Transient absorption spectroscopy measurements analyzed by global target analysis confirmed the successful charge separation with a quantum yield of 72% despite an overall small driving force of only −0.2 eV. The chargeseparated state lifetime is in the nanosecond range. Considering that 90% of the singlet excited state energy is transiently stored in the charge-separated state, we conclude a charge separation energy efficiency of 65%.